Polyester polyols from recycled polymers and waste streams

ABSTRACT

The present invention relates to polyester polyols made from aromatic polyacid sources such as thermoplastic polyesters. The polyols can be made by heating a thermoplastic polyester such as virgin polyethylene terephthalate, recycled polyethylene terephthalate, or mixtures thereof, with a glycol to give a digested intermediate which is then reacted with a digestible polymer, which can be obtained from various recycle waste streams. The polyester polyols comprise a glycol-digested polyacid source and a further digestible polymer. The polyester polyols provide a sustainable alternative to petrochemical or biochemical based polyester polyols.

FIELD OF THE INVENTION

The present invention relates to polyester polyols made from an aromaticpolyacid source, a glycol, and a digestible polymer. The polyols can bemade by heating an aromatic polyacid source with a glycol to give adigested intermediate which is then reacted with a digestible polymer,which can be obtained from various recycled polymers and low value wastestreams. The polyester polyols provide a sustainable alternative topetrochemical and biochemical based polyols, and are useful for makingother polymers.

BACKGROUND OF THE INVENTION

Polyester polyols are commonly used intermediates for the manufacture ofcondensation polymers. These condensation polymers include polyurethaneproducts such as flexible and rigid polymeric foams, polyisocyanuratefoams, coatings, powder coatings, sealants, adhesives, and elastomers.

Commonly, the polyester polyol is made by condensing aromatic diacids,diesters, or anhydrides (e.g., terephthalic acid, dimethylterephthalate) with glycols such as ethylene glycol, propylene glycol,diethylene glycol, or the like. These starting materials usually deriveexclusively from petrochemical sources.

As companies increasingly seek to offer products with improvedsustainability, the availability of intermediates produced frombio-renewable and/or recycled materials becomes more leveraging.However, there remains a need for these products to deliver equal orbetter performance than their traditional petroleum-based alternativesat a comparable price point.

Bio-renewable content alone can be misleading as an indicator of “green”chemistry. For example, when a food source such as corn is needed toprovide the bio-renewable content, there are clear trade-offs betweenfeeding people and providing them with performance-based chemicalproducts. Additionally, the chemical or biochemical transformationsneeded to convert sugars or other bio-friendly feeds to useful chemicalintermediates such as polyols can consume more natural resources andenergy, and can release more greenhouse gases and pollutants into theenvironment than their petro-based alternatives in the effort to achieve“green” status.

Waste thermoplastic polyesters, including waste polyethyleneterephthalate (PET) streams (e.g., from plastic beverage containers),provide an abundant source of raw material for making new polymers.Usually, when PET is recycled, it is used to make new PET beveragebottles, PET fiber, or it is chemically transformed to producepolybutylene terephthalate (PBT). Other recycled raw materials are alsoavailable. For example, recycled propylene glycol is available fromaircraft or RV deicing and other operations, and recycled ethyleneglycol is available from spent vehicle coolants.

Urethane formulators demand polyols that meet required specificationsfor color, clarity, hydroxyl number, functionality, acid number,viscosity, and other properties. These specifications will vary anddepend on the type of urethane application. For instance, rigid foamsgenerally require polyols with higher hydroxyl numbers than the polyolsused to make flexible foams.

Polyols suitable for use in making high-quality polyurethanes haveproven difficult to manufacture from recycled materials, includingrecycled polyethylene terephthalate (rPET). Many references describedigestion of rPET with glycols (also called “glycolysis”), usually inthe presence of a catalyst such as zinc or titanium. Digestion convertsthe polymer to a mixture of glycols and low-molecular-weight PEToligomers. Although such mixtures have desirably low viscosities, theyoften have high hydroxyl numbers or high levels of free glycols.Frequently, the target product is a purified bis(hydroxyalkyl)terephthalate (see, e.g., U.S. Pat. Nos. 6,630,601, 6,642,350, and7,192,988) or terephthalic acid (see, e.g., U.S. Pat. No. 5,502,247).Some of the efforts to use glycolysis product mixtures for urethanemanufacture are described in a review article by D. Paszun and T.Spychaj (Ind. Eng. Chem. Res. 36 (1997) 1373.

Most frequently, ethylene glycol is used as the glycol reactant forglycolysis. This is sensible because it minimizes the possible reactionproducts. Usually, the glycolysis is performed under conditionseffective to generate bis(hydroxyethyl) terephthalate (“BHET”), althoughsometimes the goal is to recover pure terephthalic acid. When ethyleneglycol is used as a reactant, the glycolysis product is typically acrystalline or waxy solid at room temperature. Such materials are lessthan ideal for use as polyol intermediates because they must beprocessed at elevated temperatures. Polyols are desirably free-flowingliquids at or close to room temperature.

The safe disposal or reuse of waste materials from various sources is anenvironmental and economic challenge. Such wastes had typically goneinto landfills, but as landfill capacity is becoming ever scarcer anddisposal costs are continuously increasing, cost effective andenvironmentally acceptable alternatives are needed to deal with thesewaste materials. Waste streams are produced by a great range ofindustries and sources, including, e.g., the plastics industry, theautomobile industry, the paper industry, consumers, the agriculturalindustry, including both crop and animal production, as well as theproduction of animal products (e.g., the dairy, egg, and woolindustries). Because of these environmental and cost challenges, thereis a need to find practical uses for recycled polymers and wastestreams. In other words, there is the need to utilize recycled polymersand waste streams to produce new polymers and building blocks for thesenew polymers.

Chemolysis, which is the chemical breakdown or decomposition of anorganic molecule into smaller molecules, may provide a route forrecycling of polymeric materials. Chemolysis is essentially adepolymerization process and can be viewed as the opposite of apolycondensation process to make a polymer. Chemolysis is usuallyapplied to condensation polymers such as PET, polyurethanes, orpolyamides. However, chemolysis is not applicable to polymers such asvinyls, acrylics, fluoroplastics and polyolefins, and by some estimatesnot applicable to more than about 10% of plastics waste. See, e.g.,“Survey of current projects for plastics recycling by chemolysis”,European Commission Joint Research Centre, Institute for ProspectiveTechnological Studies, Seville, May 1996. Therefore, the recycling orchemolysis of many recycle polymers and waste streams presentssignificant technical challenges.

In many instances, it would be highly desirable to have improvedpolyester polyols. In particular, the urethane industry needssustainable polyester polyols based in substantial part on recycledpolymers or waste streams. This scenario would provide a viable meansfor consuming these recycle waste streams. Furthermore, polyesterpolyols with high recycle content that satisfy the demanding viscosity,functionality, hydroxyl content, and performance requirements offormulators, such as polyurethane formulators, would be valuable.

It is apparent from the above there is an ongoing need for sustainablesources of polyester polyols which at the same time can help to bothreduce waste streams, and provide further options for usingunder-utilized recycled polymer streams.

SUMMARY OF THE INVENTION

The present invention relates to polyester polyols made from polyacidsources such as thermoplastic polyesters. The polyols can be made, forexample, by heating a thermoplastic polyester such as virgin PET,recycled PET, or mixtures thereof, with a glycol to give a digestedintermediate which is then reacted with a digestible or glycolyzablepolymer, e.g., a digestible or glycolyzable condensation or additionpolymer. The digestible polymer can be obtained from various recyclepolymers and waste streams. The polyester polyols can comprise aglycol-digested aromatic polyacid source, such as a glycol-digestedthermoplastic polyester and the material obtained from digestiblepolymer. The resulting polyester polyols provide a sustainablealternative to petrochemical or biochemical based polyester polyols.

We surprisingly found that high-recycle-content polyols having desirablehydroxyl numbers, viscosities, appearance, and other attributes usefulfor formulating polyurethane products can be made by reacting, atcertain equivalent ratios, a glycol-digested thermoplastic polyester,preferably a digested PET, and a digestible polymer, as defined herein.The polyols, which are valuable for formulating a variety ofpolyurethanes and related products—including polyurethane dispersions,flexible and rigid polymeric foams, coatings, powder coatings,adhesives, sealants, and elastomers—provide a sustainable alternative tobio- or petrochemical-based polyols.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a polyester polyol made by a processcomprising: (a) heating an aromatic polyacid source with a glycol togive a digested intermediate; and (b) reacting the resulting digestedintermediate with a digestible polymer containing a functional groupselected from an ester, amide, ether, carbonate, urea, carbamate,glycoside, and isocyanurate, or combinations thereof; wherein the molarratio of glycol to aromatic polyacid source is at least 0.8, and thepolyester polyol has a hydroxyl number within the range of about 10 toabout 800 mg KOH/g.

In one aspect the present invention relates to a polyester polyolwherein the aromatic polyacid source is a thermoplastic polyester.

In another aspect the present invention relates to a polyester polyolwherein the thermoplastic polyester is selected from copolymers of: (a)acids selected from terephathlic acid, 2,5-furandicarboxylic acid,isophthalic acid, dihydroferulic acid, salts thereof, C1-C6 monoestersthereof, C1-C6 diesters thereof, and combinations thereof; and (b) diolsselected from ethylene glycol, 1,2-propanediol, 1,3-propanediol,1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol,1,3-cyclohexane diol, 1,4-cyclohexane diol, 1,3-cycohexanedimethanol,1,4-cyclohexanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutane diol, andcombinations thereof.

In another aspect the present invention relates to a polyester polyolwherein the thermoplastic polyester is selected from polyethyleneterephthalate (PET), polybutylene terephthalate, polytrimethyleneterephthalate (PTT), glycol-modified polyethylene terephthalate,copolymers of terephthalic acid and 1,4-cyclohexanedimethanol,isophthalic acid-modified copolymers of terephthalic acid and1,4-cyclohexanedimethanol, copolymers of 2,5-furandicarboxylic acid orC1-C6-dialkyl 2,5-furandicarboxylates, copolymers of terephthalic acidand 2,2,4,4-tetramethyl-1,3-cyclobutane diol, and combinations thereof.

In another aspect the present invention relates to a polyester polyolwherein the thermoplastic polyester is selected from virgin PET andrecycled PET, or combinations thereof.

In another aspect the present invention relates to a polyester polyolwherein the recycled PET is obtained from recycled bottles.

In another aspect the present invention relates to a polyester polyolwherein the recycled PET is obtained from recycled textiles.

In another aspect the present invention relates to a polyester polyolwherein the recycled PET is obtained from recycled carpeting.

In another aspect the present invention relates to a polyester polyolwherein the thermoplastic polyester is selected from virgin PTT andrecycled PTT, or combinations thereof.

In another aspect the present invention relates to a polyester polyolwherein the recycled PTT is obtained from recycled textiles.

In another aspect the present invention relates to a polyester polyolwherein the recycled PTT is obtained from recycled carpeting.

In another aspect the present invention relates to a polyester polyolwherein the thermoplastic polyester is a copolymer of terephthalic acidand 2,2,4,4-tetramethyl-1,3-cyclobutane diol.

In another aspect the present invention relates to a polyol wherein theglycol is selected from ethylene glycol, propylene glycol,1,3-propanediol, 1,2-butylene glycol, 1,3-butylene glycol,1,4-butanediol, 2-methyl-1,3-propanediol, neopentyl glycol, glycerol,trimethylolpropane, 3-methyl-1,5-pentanediol, 1,4-cyclohexanedimethanol,diethylene glycol, tetraethylene glycol, dipropylene glycol, triethyleneglycol, tripropylene glycol, polyethylene glycol, polypropylene glycol,erythritol, pentaerythritol, sorbitol, and block or random copolymerglycols s of ethylene oxide and propylene oxide,or combinations thereof.

In another aspect the present invention relates to a polyester polyolwherein the glycol comprises a recycled glycol.

In another aspect the present invention relates to a polyester polyolhaving a hydroxyl number within the range of about 10 to about 800 mgKOH/g.

In another aspect the present invention relates to a polyester polyolhaving a hydroxyl number within the range of about 25 to about 500 mgKOH/g.

In another aspect the present invention relates to a polyester polyolhaving a hydroxyl number within the range of about 35 to about 400 mgKOH/g.

In another aspect the present invention relates to a polyester polyolhaving a hydroxyl number within the range of about 50 to about 400 mgKOH/g.

In another aspect the present invention relates to a polyester polyolwherein the weight percent of digestible polymer incorporated into thepolyester polyol is from about 1% to about 75%.

In another aspect the present invention relates to a polyester polyolwherein the weight percent of digestible polymer incorporated into thepolyester polyol is from about 3% to about 60%.

In another aspect the present invention relates to a polyester polyolwherein the weight percent of digestible polymer incorporated into thepolyester polyol is from about 5% to about 45%.

In another aspect the present invention relates to a polyester polyolhaving a viscosity at 125° C. less than about 5000 cP.

In another aspect the present invention relates to a polyester polyolhaving a viscosity at 25° C. less than about 20,000 cP.

In another aspect the present invention relates to a polyester polyolhaving a viscosity at 25° C. less than about 10,000 cP.

In another aspect the present invention relates to a transparentpolyester polyol.

In another aspect the present invention relates to a polyester polyolhaving a recycle content as defined herein greater than 50 wt %.

In another aspect the present invention relates to a polyester polyolwherein the aromatic polyacid source and glycol are heated in thepresence of a titanium catalyst.

In another aspect the present invention relates to a polyester polyolwherein the aromatic polyacid source and glycol are heated at atemperature within the range of about 80° C. to about 260° C.

In another aspect the present invention relates to a polyester polyolhaving an acid number of less than 10 mg KOH/g.

In another aspect the present invention relates to a polyester polyolwherein the digestible polymer is selected from digestible condensationpolymers and digestible addition polymers, or combinations thereof.

In another aspect the present invention relates to a polyester polyolwherein the digestible polymer is a digestible condensation polymer.

In another aspect the present invention relates to a polyester polyolwherein the digestible polymer is a digestible addition polymer.

In another aspect the present invention relates to a polyester polyolwherein the digestible polymer is selected from polylactic acids,synthetic (i.e. man-made) polyamides, polycarbonates, polyurethanes,polyisocyanurates, polyethers, proteins, polysaccharides, polylactones,and polylactams, or combinations thereof.

In another aspect the present invention relates to a polyester polyolwherein the digestible polymer is selected from polylactic acids.

In another aspect the present invention relates to a polyester polyolwherein the digestible polymer is selected from synthetic polyamides.

In another aspect the present invention relates to a polyester polyolwherein the digestible polymer is selected from polycarbonates.

In another aspect the present invention relates to a polyester polyolwherein the digestible polymer is selected from polyurethanes.

In another aspect the present invention relates to a polyester polyolwherein the digestible polymer is selected from polyisocyanurates.

In another aspect the present invention relates to a polyester polyolwherein the digestible polymer is selected from polyethers.

In another aspect the present invention relates to a polyester polyolwherein the digestible polymer is selected from proteins.

In another aspect the present invention relates to a polyester polyolwherein the digestible polymer is selected from polysaccharides.

In another aspect the present invention relates to a polyester polyolwherein the digestible polymer is selected from polylactones.

In another aspect the present invention relates to a polyester polyolwherein the digestible polymer is selected from polylactams.

In another aspect the present invention relates to a polyester polyolwherein the synthetic (man-made) polyamide is selected from nylon-6,nylon-6,6, nylon-6,9, nylon-6,10, nylon-6,12, nylon-11, nylon-12,nylon-4,6, and aramids, such as for example para-aramids, orcombinations thereof.

In another aspect the present invention relates to a polyester polyolwherein the synthetic polyamide is selected from virgin nylon-6,recycled nylon-6, virgin nylon-6,6, and recycled nylon-6,6, orcombinations thereof.

In another aspect the present invention relates to a polyester polyolwherein the recycled nylon-6 or the recycled nylon-6,6 is obtained fromrecycled.

In another aspect the present invention relates to a polyester polyolwherein the polycarbonate is poly(bisphenol A carbonate), also known asPBAC.

In another aspect he present invention relates to a polyester polyolwherein the polycarbonate is recycled poly(bisphenol A carbonate), alsoknown as rPBAC.

In another aspect the present invention relates to a polyester polyolwherein the protein is selected from keratin, collagen, casein, whey,zein, silk, wool or combinations thereof.

In another aspect the present invention relates to a polyester polyolwherein the protein is keratin.

In another aspect the present invention relates to a polyester polyolwherein the protein is collagen.

In another aspect the present invention relates to a polyester polyolwherein the protein is casein.

In another aspect the present invention relates to a polyester polyolwherein the protein is whey.

In another aspect the present invention relates to a polyester polyolwherein the protein is zein.

In another aspect the present invention relates to a polyester polyolwherein the protein is soy protein.

In another aspect the present invention relates to a polyester polyolwherein the protein is silk.

In another aspect the present invention relates to a polyester polyolwherein the protein is wool.

In another aspect the present invention relates to a polyester polyolwherein the keratin is selected from avian feathers.

In another aspect the present invention relates to a polyester polyolwherein the avian feathers are selected from vaned feathers and downfeathers, or combinations thereof.

In another aspect the present invention relates to a polyester polyolwherein the avian feathers are selected from chicken feathers, chickendown feathers, turkey feathers, turkey down feathers, duck feathers,duck down feathers, goose feathers, goose down feathers, or combinationsthereof.

In another aspect the present invention relates to a polyester polyolwherein the avian feathers are chicken feathers.

In another aspect the present invention relates to a polyester polyolwherein the avian feathers are chicken down feathers.

In another aspect the present invention relates to a polyester polyolwherein the avian feathers are turkey feathers.

In another aspect the present invention relates to a polyester polyolwherein the avian feathers are turkey down feathers.

In another aspect the present invention relates to a polyester polyolwherein the avian feathers are duck feathers.

In another aspect the present invention relates to a polyester polyolwherein the avian feathers are duck down feathers.

In another aspect the present invention relates to a polyester polyolwherein the avian feathers are goose feathers.

In another aspect the present invention relates to a polyester polyolwherein the avian feathers are down feathers.

In another aspect the present invention relates to a polyester polyolwherein the keratin is obtained from feather meal.

In another aspect the present invention relates to a polyester polyolwherein the polysaccharide is selected from pectin, polyglucosides, andsulphated polysaccharides, or combinations thereof.

In another aspect the present invention relates to a polyester polyolwherein the polysaccharide is pectin.

In another aspect the present invention relates to a polyester polyolwherein the polysaccharide is a polyglucoside.

In another aspect the present invention relates to a polyester polyolwherein the polysaccharide is a sulphated polysaccharide.

In another aspect the present invention relates to a polyester polyolwherein the polyglucoside is selected from starch, rayon, cellulose,hemicellulose, cellophane, and chitin, or combinations thereof.

In another aspect the present invention relates to a polyester polyolwherein the polyglucoside is starch.

In another aspect the present invention relates to a polyester polyolwherein the starch is selected from helical amylose, amylopectin, andglycogen, or combinations thereof.

In another aspect the present invention relates to a polyester polyolwherein the starch is helical amylose.

In another aspect the present invention relates to a polyester polyolwherein the starch is amylopectin.

In another aspect the present invention relates to a polyester polyolwherein the starch is glycogen.

In another aspect the present invention relates to a polyester polyolwherein the polyglucoside is rayon.

In another aspect the present invention relates to a polyester polyolwherein the polyglucoside is cellulose.

In another aspect the present invention relates to a polyester polyolwherein the polyglucoside is hemicellulose.

In another aspect the present invention relates to a polyester polyolwherein the polyglucoside is cellophane.

In another aspect the present invention relates to a polyester polyolwherein the polyglucoside is chitin.

In another aspect the present invention relates to a polyester polyolwherein the sulphated polysaccharide is carrageenan.

In another aspect the present invention relates to a polyester polyolmade by a process comprising reacting an aromatic polyacid source, aglycol, and a digestible polymer containing a functional group selectedfrom an ester, amide, ether, carbonate, urea, carbamate, glycoside, andisocyanurate group, or combinations thereof; wherein the molar ratio ofglycol to aromatic polyacid source is at least 1.0, and the polyesterpolyol has a hydroxyl number within the range of about 10 to about 800mg KOH/g.

In another aspect the present invention relates to a polyester polyolcomprising recurring units of: (a) a glycol-digested aromatic polyacidsource, and (b) an intermediate made by digesting a digestible polymercontaining a functional group selected from an ester, amide, ether,carbonate, urea, carbamate, glycoside, and isocyanurate group, orcombinations thereof.

In another aspect the present invention relates to a polyester polyolcomprising recurring units generated from: (a) an aromatic polyacidsource, and (b) a digestible polymer containing a functional groupselected from an ester, amide, ether, carbonate, urea, carbamate,glycoside, and isocyanurate group, or combinations thereof.

In another aspect the present invention relates to a polyester polyolfurther comprising recurring units of a glycol.

In another aspect the present invention relates to a polyester polyolwherein the polyacid source is other than orthophthalic acid or phthalicanhydride.

In another aspect the present invention relates to a polyester polyolwherein (a) when the polyacid source is selected from terephthalic acid,isophthalic acid, and orthophthalic acid, or esters or anhydridesthereof, or combinations of said acids, esters, or anhydrides thereof,(b) the digestible polymer contains a functional group selected from anester, amide, ether, carbonate, urea, and glycoside group, orcombinations thereof.

In another aspect the present invention relates to a polyester polyolwherein (a) when the polyacid source is selected from terephthalic acid,isophthalic acid, or esters thereof, or combinations of said acids oresters thereof, (b) the digestible polymer contains a functional groupselected from an ester, amide, ether, carbonate, urea, carbamate,glycoside, and isocyanurate group, or combinations thereof.

In another aspect the present invention relates to a polyester polyolfurther comprising a hydrophobe or nonionic surfactant, or combinationsthereof

In another aspect the present invention relates to a polyester polyolwherein the hydrophobe or nonionic surfactant is selected fromricinoleic acid, castor oil, ethoxylated castor oil, saturated orunsaturated C₉-C₁₈ dicarboxylic acids, vegetable oils, fatty acids,fatty acid esters, modified vegetable oils, fatty triglycerides,cardanol-based products, recycled cooking oil, isostearyl alcohol,hydroxy-functional materials derived from epoxidized, ozonized, orhydroformylated fatty esters, dimer fatty acids, block copolymers ofethylene oxide with propylene oxide, alkoxylated alkyl phenols,alkoxylated fatty alcohols, or combinations thereof.

In another aspect the present invention relates to a polyester polyolwherein the glycol-digested aromatic polyacid source is aglycol-digested thermoplastic polyester.

In another aspect the present invention relates to a polyurethane madefrom a polyester polyol of the present invention.

In another aspect the present invention relates to a polyurethanecomprising a polyester polyol of the present invention.

In another aspect the present invention relates to a polyurethane, priorto mixing with any other components, comprising a polyester polyol ofthe present invention

In another aspect the present invention relates to an aqueouspolyurethane dispersion made from a polyester polyol of the presentinvention.

In another aspect the present invention relates to an aqueouspolyurethane dispersion comprising a polyester polyol of the presentinvention.

In another aspect the present invention relates to a coating made from apolyester polyol of the present invention.

In another aspect the present invention relates to a coating comprisinga polyester polyol of the present invention.

In another aspect the present invention relates to a coating, prior tomixing with any other components, comprising a polyester polyol of thepresent invention.

In another aspect the present invention relates to a coating selectedfrom liquid coatings and powder coatings.

In another aspect the present invention relates to a liquid coatingcomprising a polyester polyol of the present invention.

In another aspect the present invention relates to a liquid coatingcomprising from 1% to 95% by weight of the polyester polyol of thepresent invention.

In another aspect the present invention relates to a liquid coating thatis a polyurethane coating.

In another aspect the present invention relates to a powder coatingcomprising a polyester polyol of the present invention.

In another aspect the present invention relates to a powder coating,prior to mixing with any other components, comprising a polyester polyolof the present invention.

In another aspect the present invention relates to a powder coatingcomprising from 1% to 95% by weight of the polyester polyol of thepresent invention.

In another aspect the present invention relates to a powder coatinghaving at least one glass transition temperature, Tg, greater than orequal to 45° C.

In another aspect the present invention relates to a powder coatinghaving at least one melting point greater than or equal to 45° C.

In another aspect the present invention relates to a powder coatingfurther comprising a material selected from a crosslinking agent, a flowcontrol agent, a degassing agent, a catalyst, and combinations thereof.

In another aspect the present invention relates to a powder coatingfurther comprising a pigmenting material.

In another aspect the present invention relates to a metal substratecoated with a coating material of the present invention.

In another aspect the present invention relates to a coated metalsubstrate composition comprising a metal substrate and a coatingmaterial of the present invention.

In another aspect the present invention relates to a polymeric foam madefrom a polyester polyol of the present invention.

In another aspect the present invention relates to a polymeric foamcomprising a polyester polyol of the present invention.

In another aspect the present invention relates to a polymeric foam,prior to mixing with any other components, comprising a polyester polyolof the present invention.

In another aspect the present invention relates to a polymeric foam thatis a rigid polyurethane foam.

In another aspect the present invention relates to a polymeric foam thatis a polyisocyanurate foam.

In another aspect the present invention relates to an acrylate orpolyacrylate made from the polyester polyols of the present invention.

In another aspect the present invention relates to an acrylate orpolyacrylate comprising a polyester polyol of the present invention.

In another aspect the present invention relates to a process for makinga polyester polyol comprising: (a) heating an aromatic polyacid sourcewith a glycol to give a digested intermediate; and (b) reacting theresulting digested intermediate with a digestible polymer containing afunctional group selected from an ester, amide, ether, carbonate, urea,carbamate, glycoside, and isocyanurate group, or combinations thereof;wherein the molar ratio of glycol to aromatic polyacid source is atleast 0.8, and the polyester polyol has a hydroxyl number within therange of about 10 to about 800 mg KOH/g.

In another aspect the present invention relates to a process for makinga polyester polyol comprising reacting an aromatic polyacid source, aglycol, and a digestible polymer containing a functional group selectedfrom an ester, amide, ether, carbonate, urea, carbamate, glycoside, andisocyanurate group, or combinations thereof; wherein the molar ratio ofglycol to aromatic polyacid group is at least 0.8, and the polyesterpolyol has a hydroxyl number within the range of about 10 to about 800mg KOH/g.

Definitions

As used herein, the following terms have the indicated meanings unlessexpressly stated to the contrary:

The term “digestible polymer” as used herein and described in moredetail below refers to a polymer component of the processes andcompositions of the present invention that is capable of being brokendown or degraded into smaller polymeric, oligomeric, or monomericcomponents via a chemical reaction, with the digested aromatic polyacidsource, e.g., a thermoplastic polyester, of the processes andcompositions herein. The digestible polymer is distinct from and shouldnot be confused with the aromatic polyacid source, e.g., a thermoplasticpolyester, which is also digested. An example of a chemical reaction inwhich the digestible polymer is digested or broken down is glycolysis. Avariety of digestible polymers useful herein are described below. Thesource of these polymers can be recycled polymers and waste streams.

The term “functional group” as used herein refers to specific groups ofatoms or bonds within molecules that are responsible for thecharacteristic chemical reactions or properties of those molecules. Thesame functional group will generally undergo the same or similarchemical reaction(s) regardless of the size of the molecule it is a partof. However, the relative reactivity of a functional group can bemodified by nearby functional groups and the degree of crosslinkingfound in the digestible polymer. The word moiety or the term chemicalmoiety is often used synonymously with “functional group” but, accordingto the IUPAC definition, a moiety is a part of a molecule that mayinclude either whole functional groups or parts of functional groups assubstructures. For example, an ester, —RCOOR′—, has an ester functionalgroup, —C(═O)OR—, and is composed of an alkoxy moiety, —OR′, and an acylmoiety, RC(═O)—, or, equivalently, an ester functional group may bedivided into carboxylate, RC(═O)O—, and alkyl, —R′, moieties. Note thatR and R′ represent the remainder of the molecule to which the functionalgroup or moiety is attached, in this example R and R′ beingcarbon-containing groups such as alkyl groups. Nonlimiting examples offunctional groups include those found in the digestible polymers of thepresent invention:

Ester, or —C(═O)O— (in this instance the O— is attached to the carbon ofa carbon containing chemical group);

Amide, or —C(═O)NR—, in this instance R is H or a carbon-containinggroup;

Ether, —ROR′—, in this instance R and R′ are independently the same ordifferent carbon-containing groups;

Carbonate, —OC(═O)O—;

Urea, also known as carbamide, —NRC(═O)NR′—, in this instance R and R′are independently H or a carbon-containing group;

Carbamate, also known as urethane, —OC(═O)NR—, in this instance R is Hor a carbon-containing group;

Glycoside, i.e. a molecule in which a sugar is bound to another sugar orfunctional group via a glycosidic linkage. The following chemicalstructure of the compound sucrose, is a nonlimiting example,illustrating the glycosidic linkage of the sugars glucose and fructosein the dissacharide sucrose.

Sucrose Molecule Illustraing Glycosidic Linkage

Isocyanurate, i.e. a 6-membered ring system containing alternatingsubstituted nitrogen and carbonyl groups, that is usually derived from adiisocyanate. In this instance R and R′ are independently selected froma carbon-containing group.

The term “glycolysis” as used herein is from the field of polymerchemistry where it refers to the digestion of a polymer with a glycolvia a chemical reaction to yield lower molecular weight fragments, suchas for example, oligomers and monomers.

The terms “waste stream” as used herein refers to waste or discardedproducts from industry, agriculture, or consumer sources that has fewultimate destinations or applications other than for example, landfill,incineration, animal feed, concrete, burning as a source of energy,fertilization, landscaping mulch, or other relatively low valueapplications.

The term “recycled polymer” as used herein refers to a polymer that haslittle value after its original lifespan has ended, and is recovered inan economically viable fashion from the original spent application foruse in other applications.

Digestible Polymers

The compositions and processes of the present invention comprise adigestible polymer. These digestible polymers have or contain afunctional group selected from ester, amide, ether, carbonate, urea(i.e. carbamide), carbamate (i.e. urethane), glycoside, and isocyanurategroups, or combinations thereof. The digestible polymers are such thatthey are capable of being “digested” or broken down or degraded intosmaller polymeric, oligomeric, or monomeric components via a chemicalreaction, which can include an enzymatic reaction.

The digestible polymers can be selected from condensation polymers,addition polymers, or combinations thereof. Condensation polymers areformed via a condensation reaction where the monomers are joinedtogether and lose a small molecule, such as water, ammonia, or a lowmolecular weight alcohol, e.g., methanol or ethanol, as a byproduct.Addition polymers are formed via the chemical addition of monomerswithout the loss of a small molecule byproduct. For the purposes of thisinvention, addition polymers are generally made by the ring opening andaddition of monomers such as lactones, lactams and epoxides to aninitiator molecule such as an amine or alcohol, by the addition ofmonomers such as di- or poly-isocyanates to active hydrogen containingpolyols or amines to form polyurethanes, or by the trimerization of di-or poly-isocyanates to form isocyanurates.

The digestible polymers of the present invention are selected frompolylactic acids (PLAs), synthetic polyamides, polycarbonates,polyurethanes, polyisocyanurates (PR), polyethers, proteins,polysaccharides, or combinations thereof. Of the foregoing, thepolylactic acids (PLAs), synthetic polyamides, polycarbonates, proteins,and polysaccharides are generally considered condensation polymers.However, polylactones, which are made from lactone monomers such as, forexample caprolactone, and polylactams, which are essentially polyamidesthat have been made from lactam monomers such as, for examplecaprolactam, are generally considered addition polymers. Polyethers maybe prepared via the condensation of alcohols, however, they are usuallyprepared by the addition reaction of monomers such as ethylene oxide,propylene oxide and tetrahydrofuran to active hydrogen-containinginitiators such as alcohols, glycols or amines. Additionally, polylacticacid may be prepared via the either the addition reaction of lactide toactive hydrogen containing inititators or the condensation reaction oflactic acid with itself. Finally, polyurethanes and polyisocyanurates(PIR) are usually prepared via the addition polymerization of a di- orpoly-isocyanurate with an active hydrogen substance such as a polyol oramine, or via the dimerization or trimerization of di- orpoly-isocyanates to form uretidine diones and isocyanurates,respectively. It should also be noted that the characterization of thepolymers according to the foregoing categories is conventional and forconvenience. However, it is recognized that there is some overlapamongst the categories. For example, polyamides, polylactams, andproteins all contain amide functional groups, even though forconvenience, they are being described separately. Similarly, polylacticacids and polylactones both contain ester functional groups.Furthermore, the digestible polymers can contain more than one type offunctional group.

Examples of such polymers containing multiple functional groups arepolyurethanes and polyisocyanurates, which may contain ether, ester,urethane and isocyanurate groups. Other digestible polymers are blockcopolymers having repeating blocks or segments of different polymerizedmonomers. Also, alloys, blends, composites or combinations of more thanone kind of digestible polymer are within the scope of the presentinvention.

It should be noted that the digestible polymers as described herein inthis section are considered separate from and are a distinct componentof the present invention, from the materials described in the “AromaticPolyacid Source” section, below.

The digestible polymers can be obtained from recycled polymers and wastestreams. In fact, in view of green chemistry and sustainabilityconsiderations, it is highly desirable to use digestible polymers fromsuch sources. The digestible polymer may further be obtained from virginor newly manufactured sources. This latter choice makes sense in caseswhere the additional performance benefit obtained by digesting the newlymanufactured polymer provides a value-added benefit to the resultingpolyester polyol product.

Digestion Medium for the Digestible Polymer

The digestible polymers can be digested with a material from thedigestion of an aromatic polyacid source. Various polyacid sources areuseful for being digested to provide the digestion medium, including athermoplastic polyester. Examples of such thermoplastic polyestersinclude polyethylene terephthalate (PET), polybutylene terephthalate,polytrimethylene terephthalate, glycol-modified polyethyleneterephthalate, copolymers of terephthalic acid and1,4-cyclohexanedimethanol, isophthalic acid-modified copolymers ofterephthalic acid and 1,4-cyclohexanedimethanol, copolymers of2,5-furandicarboxylic acid or dialkyl 2,5-furandicarboxylates, orcombinations thereof. One or more glycols can also be used with thematerial described above in this paragraph. These glycols can be thesame as those described below in the “Glycols” section. Examples ofpreferred glycols include ethylene glycol, propylene glycol, diethyleneglycol, and polyethylene glycols with molecular weights less than about400, and combinations thereof.

Also, as described herein, the polyester polyols can be made in a onepot or one reactor system in which the polyacid source, the glycol, andthe digestible polymer are combined such that the polyacid source andthe glycol form the digestion material in the presence of the digestiblepolymer and thus digest the digestible polymer.

The following are examples of digestible polymers useful herein.

Polylactic Acids (PLAs)

Polylactic acids (PLAs) are digestible polymers useful herein.Polylactic acids are thermoplastic aliphatic polyesters. They arebiodegradable and are usually derived from renewable resources, such ascorn starch; tapioca roots, chips or starch, or sugarcane. In 2010, PLAhad the second highest consumption volume of any bioplastic in theworld. See, Market Study Bioplastics, Ceresana, December 2011. Anexample of a polylactic acid useful herein includes Ingeo polylacticacid, supplied by Natureworks LLC. Although the recycle of PLA is in itsinfancy, examples exist such as closed loop recycling in sportsstadiums, where cups, utensils and other food and beverage packagingwithin the stadium are entirely based on PLA, permitting ease ofrecycle.

Synthetic Polyamides

Synthetic, i.e. man-made polyamides are digestible polymers usefulherein. These polymers have repeating units linked by amide functionalgroups. The term “synthetic” or “man-made”, as used herein is todistinguish these digestible polymers from the proteins, which contain“amide” or “peptide” linkages, described below. Synthetic polyamides canbe made through step-growth polymerization or solid-phase synthesis,examples being nylons, aramids, and sodium poly(aspartate). Syntheticpolyamides are commonly used in textiles, automotives, carpet andsportswear due to their extreme durability and strength. Examples ofman-made polyamides useful herein include the nylons such as nylon-6,nylon-6,6, nylon-6,9, nylon-6,10, nylon-6,12, nylon-11, nylon-12,nylon-4,6, and the aramids and para-aramids such as Kevlar, Technora,Twaron, Heracron, and Nomex. An example of a biobased polyamide includesPA 11, which is a biopolymer derived from natural oil. It is supplied byArkema under the tradename Rilsan B. A similar biobased polyamide isPolyamide 410 (PA 410), derived from castor oil produced by DSM underthe trade name EcoPaXX. Sources of recycled polyamides include nylonscrap from industry including injection molded automotive parts andpost-consumer or post industrial scrap or waste such as textiles,fabrics and nylon carpet.

Polycarbonates

Polycarbonates are digestible polymers useful herein. Polycarbonates arepolymers containing repeating units connected by carbonate functionalgroups. Many polycarbonates of commercial interest are derived fromrigid monomers. A balance of useful features including temperatureresistance, impact resistance and optical properties positionpolycarbonates between commodity plastics and engineering plastics.Polycarbonates can be produced by the reaction of bisphenol A (BPA) andphosgene. The resulting polymer is known as poly(bisphenol A carbonate),i.e. PBAC. It is found that recycled poly(bisphenol A carbonate), i.e.rPBAC, can also be used in the digestion. Furthermore, we have foundthat poly(bisphenol A carbonate) can be transreacted with rPET contentpolyols to form poly(ester/carbonate) hybrid polyols. Although thechemolysis of polycarbonates is known, none of the scientific worksstudied the use of aromatic polyester polyols as glycolyzing agents forrPBAC. See A. Oku, S. Tanaka, S. Hata, Polymer 41 (2000) 6749-6753; D.Kim, B., Kim, Y. Cho, M. Han, B., Kim, Ind. Eng. Chem. Res. (2009), 48,685-691; and C. Lin, H. Lin, W. Liao, S.A. Dai, Green Chemistry, (2007),9, 38-43.

Examples of polycarbonates useful here include Lexan®, Calib®, andMakrolon®. Polycarbonate is coded 7 implying that it is difficult torecycle, however, polycarbonate bottles and CDs are being extensivelyrecycled. One method of recycling polycarbonate is by chemicalrecycling. PC is made to react with phenol in the presence of a catalystto form BPA and DPC monomers. After purification, both these monomersare used to produce the polymer. The current invention provides animproved method for recycling polycarbonate thermoplastics.

Polyurethanes

Polyurethanes (PUs or PURs) are digestible polymers useful herein.Polyurethanes are polymers composed of a chain of organic units joinedby carbamate (urethane) linkages. Most polyurethanes are thermosettingpolymers that do not melt when heated, however, thermoplasticpolyurethanes are also available. Polyurethanes are typically formed byreacting a di- or polyisocyanate with a polyol. Both the isocyanates andpolyols used to make polyurethanes contain on average two or morefunctional groups per molecule. Polyurethanes are used in themanufacture of many commercially important items, including flexible,high-resilience foam seating; rigid foam insulation panels;microcellular foam seals and gaskets; durable elastomeric wheels andtires; automotive suspension bushings; electrical potting compounds;high performance adhesives; surface coatings; powder coatings; sealants;synthetic fibers (e.g., Spandex); carpet underlay; hard-plastic parts(e.g., for electronic instruments); and hoses. Polyurethane products canbe recycled in various ways to remove them from the waste stream and torecapture some of the value inherent in the original material.Polyurethane recycle streams can result on job sites, from scrap PU orPIR during industrial production of flexible or rigid foam products andduring building demolition. Examples of PU recycle methods includerebond to form carpet underlay, digestion via glycols to provide usefulpolyols, grinding PU products into powder for blending back into theoriginal PU product and compression molding of scrap PU into usefularticles. Thus, recycle or scrap PU streams exist that can be utilizedin the practice of this invention.

Polyisocyanurates (PIRs)

Polyisocyanurates (PIRs) are digestible polymers useful herein.Polyisocyanurates are typically produced as a foam and used as rigidthermal insulation. It is commonly used in the building industry forbuilding and pipe insulation. Scrap or recycle streams of PR areavailable from building demolition, from industrial production of PIRfoams, scrap from the manufacture of new buildings or the retrofittingof new insulation into existing structures. Thus, recycle or scrap PIRstreams exist that can be utilized in the practice of this invention.

Polyethers

Polyethers are digestible polymers useful herein. These polymers containrepeating units linked together by ether functional groups. Examples ofsuch polyethers include polyethylene glycol (PEG), polypropylene glycol(PPG), polytetramethylene glycol (PTMG), and mixed PEG/PPG polymers.Since PU and PIR polymers utilize polyether polyols, the same recyclestreams as exist for those polymers exist for polyethers. Additionally,it is conceivable that post-industrial streams exist for off-grade orscrap nonionic surfactants and polyether polyols that could be utilizedfor the practice of this invention.

Proteins

Proteins are digestible polymers useful herein. Proteins are naturallyoccurring polymeric materials made of amino acids linked together bypeptide, i.e. amide groups. In other words, proteins are largebiological molecules, or macromolecules, consisting of one or more longchains of amino acid residues. Proteins perform a vast array offunctions within living organisms, including catalyzing metabolicreactions, replicating DNA, responding to stimuli, and transportingmolecules from one location to another, and providing structure and massto living organisms. Proteins differ from one another primarily in theirsequence of amino acids, which is dictated by the nucleotide sequence oftheir genes, and which usually results in folding of the protein into aspecific three-dimensional structure that determines its function andactivity. Proteins are also found combined with fats and are referred toas lipoproteins and with polysaccharides and are referred to asglycoproteins. The proteins are described separately herein from theman-made polyamides described above.

Proteins are found in a wide variety of agricultural materials, plants,and animals.

Proteins and their use as recycle or waste streams are further describedin “Proteins in Biomass Streams: A study commissioned by theBiorenewable Resources Platform (Platform Groene Grondstoffen), authoredby Wim Mulder and dated April 2010, which is incorporated by referenceherein in its entirety. Examples of proteins include keratin, collagen,milk proteins such as casein and whey, zein, silk and wool.

Keratin is a family of fibrous structural proteins. Keratin is the keystructural material making up the outer layer of human skin. It is alsothe key structural component of hair and nails. Keratin monomers areassembled into bundles to form intermediate filaments, which are toughand insoluble and form strong unmineralized tissues found in reptiles,birds, amphibians, and mammals. A form of keratin called alpha-keratinis composed of alpha-coils and globular sections, and is the maincomponent of hair, wool, nails, horns, and hooves. A form of keratincalled beta-keratin, in which the protein strands are hydrogen-bondedinto pleated sheets are found in the feathers, beaks and claws of birdsand the and the claws, scales and shells of reptiles. Silk is also anexample of keratin.

A digestible polymer source useful herein is avian, i.e. bird, feathers,which include the tougher outer or vane (also vaned, vein, or veined)feathers of birds and the softer inner, or juvenile feathers (alsocalled down or down feathers). The poultry, both meat and egg producing,industries generate a large amount of waste feathers and down. Thus birdfeathers such as chicken feathers, chicken down, duck feathers, duckdown, goose feathers, goose down, turkey feathers, and turkey down, arean abundant and renewal source of digestible keratin polymers. SeeBumla, N. A., et al., Process and Utilization of Feathers, PoultryTechnology, Jul. 28, 2012; V. Saucedo-Rivalcoba, et al., (Chickenfeathers keratin)/polyurethane membranes, Applied Physics A (2011) 104:219-228; A. Ullah, et al., Bioplastics from Feather Quill,Biomacromolecules 2011, 12 3826-3832; and PCT Patent ApplicationPublication No. WO 2014/023684 A1, to Nestec S. A., published Feb. 13,2014; which are incorporated by reference herein in their entirety.Feather meal is a byproduct of processing poultry. It is made frompoultry feathers by partially hydrolyzing them under elevated heat andpressure, and then grinding and drying them. Although total nitrogenlevels are fairly high (up to 12%), the bioavailability of this nitrogenmay be low. Feather meal is used in formulated animal feed and as anorganic fertilizer. Feather meal is made through a process calledrendering. Steam pressure cookers with temperatures over 140° C. areused to “cook” and sterilize the feathers. This partially hydrolyzes theproteins, which denatures them. It is then dried, cooled and ground intoa powder for use as a nitrogen source for animal feed (mostly ruminants)or as an organic soil amendment. In certain instances feather meal canbe particularly well suited for digestion as it can digest morecompletely than whole feathers.

Collagen is a fibrous, structural protein that is found in animaltissue, such as skin, bones, and tendons. The basic structure is atriple helix made up from three polypeptide chains, and has a commonrepeating unit of glycine, proline, and hydroxyproline. Collagen isreadily available as a recycle stream from the livestock processingindustry.

Milk proteins such as casein and whey are a major component of dairyproducts and represent a recycle stream from the dairy industry. Caseinsare primarily phosphoproteins and are characterized by an open, randomcoil structure. Whey has a protein content of about 75-80% and is aby-product from cheese production and is rich in beta-lactoglobulin.

A variety of proteins are available from plant sources, including theimportant crops such as wheat, maize (corn), soy, potatoes, and otherlegumes such as peas. For example, a number of different proteins arefound in maize (corn) including albumin, globulin, zein (a class ofprolamine proteins), and glutelin. A number of proteins are also foundin wheat, including albumin, globulin, and glutenins. Gluten is the mainstorage protein in wheat. Soy flour is made from roasted soybeans groundinto a fine powder and contains 50 percent protein. Soy flour comes inthree forms: natural or full-fat, defatted, and lecithinated. Natural orfull-fat contains natural oils found in the soybean. Defatted has theoils removed during processing. Lecithinated has lecithin added. Soyflour is gluten-free, so yeast-raised breads made with soy flour aredense in texture. Soy grits are similar to soy flour except that thesoybeans have been toasted and cracked into coarse pieces. Defatted soyflour is made entirely from defatted soy meal. Defatted soy flour isused as an ingredient and supplement to cereal products (wheat, corn,rice). It can be used in a wide variety of products including bread,weaning foods, cereals, cookies, muffins, cereals, cakes, pastas, andtortillas. It is currently being used worldwide by commercialprocessors. It is also a common ingredient in blended food aid products,such as Corn-Soy blend, Soy fortified wheat flour, et al. Defatted soyflour can also be fortified with various micronutrients and minerals. Itshould be recognized that soy flour is both a source of soy protein aswell as carbohydrates. The nutrient data per 100 grams of uncookeddefatted soy flour is reported as: moisture 9 g, Protein (N×6.25)moisture-free basis 52 g, ash 6 g, fat (petroleum ether) 1 g, fat (acidhydrolysis) 3 g, crude fiber 4 g, total dietary fiber 18 g, and totalcarbohydrates 30 g.

Wool is a fibrous protein fiber obtained from sheep and certain otheranimals, including cashmere from goats, mohair from goats, qiviut frommuskoxen, angora from rabbits, and other types of wool from camelids.

Also, proteins can be obtained from aquatic sources such as fish,microalgae, and macroalgae (seaweed). Therefore, such materials areavailable from fish processing and seaweed farming.

Polysaccharides

Polysaccharides are digestible polymers useful herein. Polysaccharidesare polymeric carbohydrate molecules composed of long chains ofmonosaccharide units bound together by glycosidic linkages. Thepolysaccharide chains can be linear or branched and include storagepolysaccharides such as starch and glycogen, and structuralpolysaccharides such as cellulose and chitin. Polysaccharides include,e.g., polyglucosides (that is polymers of glucose) and sulphatedpolysaccharides. Examples of polyglucosides include starch, rayon,cellulose, cellophane, and chitin. Starch can be further characterizedby the categories of helical amylose, amylopectin, and glycogen. Chitinis a polymeric material of N-acetylglucosamine, a derivative of glucose.Chitin is the main component of the cell walls of fungi, theexoskeletons of arthropods such as crustaceans (e.g., crabs, lobstersand shrimp) and insects, the radulae of molluscs, and the beaks andinternal shells of cephalopods, including squid and octopuses. Thestructure of chitin is generally of crystalline nanofibrils or whiskers.Chitin is available as a recycle stream from the shellfish industry. Anexample of a sulphated polysaccharide is carrageenan, which is a linearpolymer extracted from red edible seaweeds. Cellulose is an organiccompound with the formula (C₆H₁₀O₅)_(n), where “n” indicates the numberof repeating formula units It is a polysaccharide consisting of a linearchain of several hundred to many thousands of β(1→4) linked D-glucoseunits. Cellulose is an important structural component of the primarycell wall of green plants, many forms of algae and the oomycetes. Somespecies of bacteria secrete it to form biofilms. Cellulose is the mostabundant organic polymer on Earth. The cellulose content of cotton fiberis 90%, that of wood is 40-50% and that of dried hemp is approximately45%. Cellulose is mainly used to produce paperboard and paper. Smallerquantities are converted into a wide variety of derivative products suchas cellophane, rayon and nitrocellulose. Cellulose for industrial use ismainly obtained from wood pulp, cotton and recycled paper products.

A polysaccharide useful herein is pectin. As described in sources suchas Wikipedia, pectin is a structural heteropolysaccharide contained inthe primary cell walls of terrestrial plants and was first isolated anddescribed in 1825 by Henri Braconnot. Pectins are rich in galacturonicacid, and several distinct polysaccharides have been identified andcharacterised within the pectic group. Homogalacturonans are linearchains of α-(1→4)-linked D-galacturonic acid. Substituted galacturonansare characterized by the presence of saccharide appendant residues (suchas D-xylose or D-apiose in the respective cases of xylogalacturonan andapiogalacturonan) branching from a backbone of D-galacturonic acidresidues. Rhamnogalacturonan I pectins (RG-I) contain a backbone of therepeating disaccharide: 4)-α-D-galacturonic acid-(1,2)-α-L-rhamnose.Another structural type of pectin is rhamnogalacturonan II (RG-II),which is a less frequent, complex, highly branched polysaccharide.Rhamnogalacturonan II is classified by some authors within the group ofsubstituted galacturonans since the rhamnogalacturonan II backbone ismade exclusively of D-galacturonic acid units. Isolated pectin has amolecular weight of typically 60,000-1.30,000 g/mol, varying with originand extraction conditions. See U.S. Pat. No. 4,520,139, to Kennedy etal, issued May 28, 1985.

Polylactones and Polylactams

Polylactones and polylactams are digestible polymers useful herein. Anexample of a polylactone is a polymer made by the addition orring-opening polymerization of caprolactone. An example of a polylactamis a polymer made by the polymerization of caprolactam. The polylactonesare polyesters that contain multiple ester functional groups. Similarly,the polylactams are essentially polyamides, because they containmultiple amide functional groups as if they were instead derived fromamino substituted carboxylic acids. Nylon-6, even though listed in thepolyamide section, above, is essentially a polylactam made from the ringopening or addition polymerization or addition of caprolactam monomers.A possible source of recycled polylactone includes post-industrial scrapfrom polyurethane elastomer product manufacturing.

Glycols

Glycols suitable for use are well known. By “glycol,” we mean a linearor branched, aliphatic or cycloaliphatic compound or mixture ofcompounds having two or more hydroxyl groups. Other functionalities,particularly ether or ester groups, may be present in the glycol. Inpreferred glycols, two of the hydroxyl groups are separated by fromabout 2 to about 20 carbons, preferably from about 2 to about 14 carbonatoms, and more preferably from about 2 to about 8 carbons. Note thatether linkages may be included in the carbon separation between hydroxylgroups, though the oxygen atoms are not included in the carbon count.Suitable glycols include, for example, ethylene glycol, propyleneglycol, 1,3-propanediol, 1,2-butylene glycol, 1,3-butylene glycol,1,4-butanediol, 2-methyl-1,3-propanediol, neopentyl glycol, glycerol,trimethylolpropane, 3-methyl-1,5-pentanediol,1,4-cyclohexane-dimethanol, diethylene glycol, dipropylene glycol,triethylene glycol, 1,6-hexanediol, tripropylene glycol, tetraethyleneglycol, polyethylene glycols (PEGs), polypropylene glycols (PPGs),erythritol, pentaerythritol, sorbitol, and block or random copolymerglycols of ethylene oxide and propylene oxide, and the like, andmixtures thereof. Preferably, the glycol is selected from ethyleneglycol, propylene glycol, 2-methyl-1,3-propanediol, diethylene glycol,3-methyl-1,5-pentanediol, neopentyl glycol, and polyethylene glycolswith molecular weights less than about 600 (e.g., PEG 200 and PEG 400),and mixtures thereof. Propylene glycol is particularly preferred. In apreferred aspect, the glycol is a recycled glycol, especially propyleneglycol and recycled diethylene glycol. Propylene glycol recovered fromused deicing fluids is one example. In another preferred aspect, theglycol is a recycled ethylene glycol, which may be recovered from usedengine antifreeze or coolant.

Aromatic Polyacid Source

The term “aromatic polyacid source” is used to designate that thematerial or source contains one or more aromatic acid moieties orgroups. Chemical Structure 1, below, provides an illustration of anAromatic Polyacid Source.

Where R₁ and R₂ are carboxylate groups; and R₃ and R₄ are selected fromcarboxylate group or hydrogen.

Chemical Structure 2, below provides another illustration of an AromaticPolyacid Source.

Where both R groups are carboxylic acid groups or alkyl ester groups.

Chemical Structure 3, below, provides another illustration of anAromatic Polyacid Source.

Where R₁ and R₂ are selected independently from either an alkyl group orhydrogen.

It should be noted that the aromatic polyacid source materials asdescribed herein in this section are considered separate from and are adistinct component of the present invention, from the digestiblepolymers, as described separately in the “Digestible Polymers” section,above.

The aromatic polyacid source includes polyesters such as thermoplasticpolyesters. These include polyesters polymers prepared by the reactionof one or more difunctional and/or multifunctional aromatic carboxylidacids with one or more difunctional hydroxyl compounds and/ormultifunctional hydroxyl compounds.

Examples of materials that contain aromatic polyacid groups suitable forthe practice of the invention include phthalic acid, phthalic anhydride,dimethyl phthalates, dialkyl phthalates, terephthalic acid, dimethylterephthalates, dialkyl terephthalate, isophthalic acid, dimethylisophthalates, dialkyl isophthalates, DMT bottoms (for example, asdescribed in U.S. Pat. No. 5,075,417; U.S. Pat. No. 4,897,429; U.S. Pat.No. 3,647,759; U.S. Pat. No. 4,411,949; U.S. Pat. No. 4,714,717; andU.S. Pat. No. 4,897,429), trimellitic acid, trimellitic anhydride,trimethyl trimellitate, naphthalene dicarboxylic acid, pyromelliticanhydride, 2,5-furandicarboxylic acid, dialkyl 2,5-furandicarboxylate,pyromellitic acid, dialkyl naphthalene dicarboxylate, and mixturesthereof.

Also, the term “terephthalic acid” is intended to include terephthalicacid itself and residues thereof as well as any derivative ofterephthalic acid, including its associated acid halids, esters,half-esters, salts, half-stats, anhydrides, mixed anhydrides, ormixtures thereof or residues thereof useful in a reaction process with adiol to make a polyester.

Aromatic polyacid sources may also be obtained from thermoplasticpolyesters. Thermoplastic polyesters suitable for use are well known inthe art. They are condensation polymers produced from the reaction ofglycols and aromatic dicarboxylic acids or acid derivatives. Examplesinclude polyethylene terephthalate (PET), polybutylene terephthalate(PBT), polytrimethylene terephthalate (PTT), glycol-modifiedpolyethylene terephthalate (PETG), copolymers of terephthalic acid and1,4-cyclohexanedimethanol (PCT), copolymers of 2,5-furandicarboxylicacid or dialkyl 2,5-furandicarboxylates and at least one glycol, PCTA(an isophthalic acid-modified PCT), copolymers of naphthalenedicarboxylic acid or dialkyl naphthalene dicarboxylate and the like, andmixtures thereof.

Suitable thermoplastic polyesters include virgin polyesters, recycledpolyesters, or mixtures thereof. Polyethylene terephthalate (PET) isparticularly preferred, especially recycled polyethylene terephthalate(rPET), virgin PET, and mixtures thereof. For more examples of suitablethermoplastic polyesters, see U.S. Pat. Appl. Publ. No. 2009/0131625,the teachings of which are incorporated herein by reference.

Recycled polyethylene terephthalate suitable for use in making theinventive polyester polyols can come from a variety of sources. The mostcommon source is the post-consumer waste stream of PET from plasticbottles or other containers. The rPET can be colorless or contain dyes(e.g., green, blue, brown, or other colors) or be mixtures of these. Aminor proportion of organic or inorganic foreign matter (e.g., paper,other plastics, glass, metal, etc.) can be present. A desirable sourceof rPET is “flake” rPET, from which many of the common impuritiespresent in scrap PET bottles have been removed in advance. Anotherdesirable source of rPET is pelletized rPET, which is made by meltingand extruding rPET through metal filtration mesh to further removeparticulate impurities. Because PET plastic bottles are currentlymanufactured in much greater quantity than any recycling efforts canmatch, scrap PET will continue to be available in abundance. Othersources of PET include, PET textiles and PET carpeting, such as recycledPET textiles and recycled PET carpeting. For example, recycled PETpolyester carpet including polyolefin backing, calcium carbonate filler,and latex adhesive, assuming an approximate PET composition of 90% ofthe carpet, is a useful source material to prepare the digestedintermediate.

Polytrimethylene terephthalate (PTT) is another useful polyaromaticsource, and like PET, can be obtained from PTT textiles and PTTcarpeting, such as recycled PTT textiles and recycled PTT carpeting. Forexample, recycled PTT polyester carpet including polyolefin backing,calcium carbonate filler, and latex adhesive, assuming an approximatePTT composition of 90% of the carpet, is a useful source material toprepare the digested intermediate.

Other useful polyaromatic sources are polyesters made from polyaromaticsand rigid diols such as cycloalkane diols, examples of such rigid diolsincluding 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,3-cycohexane diol,1,4-cyclohexane diol, 1,3-cyclohexanedimethanol, and1,4-cyclohexanedimethanol. Such examples include terephthalatecopolyesters of 2,2,4,4-tetramethyl-1,3-cyclobutanediola, and alsopolyesters which also contain flexible diols, such as C2-C6 linear orbranched aliphatic diols. Examples of these polyesters include, forexample Eastman Tritan materials from post-consumer recycle of waterbottles See, also, U.S. Patent Application No. US 2013/0072628 A1, toCrawford et al., published Mar. 21, 2013; and D. R. Kelsey et al., HighImpact, Amorphous Terephthalate Copolyesters of Rigid2,2,4,4-Tetramethyl-1,3-cyclobutanediol with Flexible Diols,Macromolecules, 2000, 33, 5810-5818; which are incorporated by referenceherein in their entirety.

Hydrophobes and Nonionic Surfactants

The polyester polyols of this invention may also comprise hydrophobes,nonionic surfactants, and mixtures thereof. Hydrophobes includetriglycerides and modified triglycerides, fatty acids, fatty acidesters, dimer fatty acids, fatty diacids, vegetable oils and modifiedvegetable oils (for example as described in U.S. Pat. No. 5,922,779,U.S. Pat. No. 6,359,022, U.S. Pat. No. 6,664,363, and WO 2013/154874A1);castor oil (for example, as described in WO 2013/154874A1); modified orderivatized polyterpenes; modified cashew nut shell oil; cardanol;derivatives of cardanol; Diels Alder or ene reaction modified polyols(for example, as described in WO 2013/109834); and tall oil fatty acids(for example, as described in U.S. Pat. No. 5,075,417 and U.S. Pat. No.4,897,429). The aromatic polyester polyols may further comprise nonionicsurfactants or reactants (for example, as described in U.S. Pat. No.4,529,744, WO 9919377 and WO 2009045926).

Examples of triglycerides suitable for the practice of this inventioninclude soybean oil, animal tallow, fish oil, canola oil, castor oil,tung oil, linseed oil, corn oil, recycled cooking oil, sunflower oil,palm oil, peanut oil, palm kernel oil, cottonseed oil, coconut oil, andsafflower oil.

Examples of fatty acids suitable for the practice of this inventioninclude linoleic, myristic, palmitic, caproic, caprylic, capric, 2-ethylhexanoic, lauric, stearic, oleic, linolenic, ricinoleic, tall oil, andmixtures thereof. The alkyl esters of these fatty acids and mixtures ofthese alkyl esters thereof are also suitable examples for the practiceof this invention.

Examples of fatty diacids suitable for the practice of this inventioninclude azelaic acid; sebacic acid; dodecanedioic acid; tetradecanedioicacid; hexadecanedioic acid; octadecanedioic acid; nonene dioic acid;decenedioic acid, dodecenedioic acid; tetradecenedioic acid;hexadecenedioic acid; octadecenedioic acid; eicosendioic acid;eicosandioic acid; docosandioic acid; tetracosandioic acid;tetracosendioic acid; and the like and mixtures thereof.

Examples of nonionic surfactants include block copolymers of ethyleneoxide with either propylene oxide, butylene oxide, or mixtures ofpropylene oxide with butylene oxide. See “nonionic Surfactants:Polyoxyalkylene Block Copolymers”, (Surfactant Science Series, Book 60,CRC Press), 1996, Vaughn Nace, ed. And “Nonionic Surfactants: OrganicChemistry” (Surfactant Science Series Book 72), 1997 Nico M. van Os.,ed. It is well known that initiators are used to initiate such blockcopolymers. Suitable initiators include glycols; monols; fatty alcohols;alkyl phenols; phenol; styrenated phenols; bisphenols; triols; andtetrols. An additional nonionic surfactant suitable for use as areactant or additive includes ethoxylated or alkoxylated castor oil.

Catalysts

Catalysts suitable for making the digested intermediate are well known(see, e.g., K. Troev et al., J. Appl. Polym. Sci. 90 (2003) 1148). Inparticular, suitable catalysts comprise titanium, zinc, antimony,germanium, zirconium, manganese, or other metals. Specific examplesinclude titanium alkoxides (e.g., tetrabutyl titanate), titanium(IV)phosphate, zirconium alkoxides, zinc acetate, lead acetate, cobaltacetate, manganese(II) acetate, antimony trioxide, germanium oxide, orthe like, and mixtures thereof. Catalysts that do not significantlypromote isocyanate reaction chemistries are preferred. The amount ofcatalyst used is typically in the range of 0.005 to 5 wt. %, preferably0.01 to 1 wt. %, more preferably 0.02 to 0.7 wt. %, based on the totalamount of polyol being prepared.

The hydrolysis and chemolysis of the digestible polymer can be catalyzedby the use of enzymes such as proteases; lipases; amylases; maltases;sucrases; lactases; esterases; hydrolases; amidases; glycosidases;glycoside hydrolases; peptidases and the like and mixtures thereof.Subsequent reaction of the resulting hydrolysis or chemolysis productswith the digested intermediate may then be facilitated by enzymes suchas lipases; amidases and esterases.

The reaction of the digestible polymer with the digested intermediatecan also be catalyzed by the use of acids or bases, including carboxylicacids.

Processes, Properties and Compositions

The present invention provides a means for recycling both the aromaticacid source and the digestible polymer to provide a polyester polyolhaving a high recycle content. The recycle content of the resultantpolyester polyol can have a wide range of recycle content, but thosehaving a recycle content of about 50% by weight or more would beparticularly attractive.

With respect to recycle streams, when the material is nylon-6,nylon-6,6, or PTT carpet, the fibers typically originate aspost-industrial off-grade or defective recycle carpet, greige goods, orfiber products and post-consumer recycle carpet. In the case ofpost-consumer recycled carpet, the carpet is typically collected bycarpet un-installers for use as a recycle stream. This stream has morecontaminants such as dirt, pet hair, mold and the like than apost-industrial recycle carpet stream, and may require a washing step inconventional recycling schemes prior to use as a recycled nylon-6,nylon-6,6, or PTT stream. Hence, a process, as in the present invention,that circumvents the need for a wash step would represent an improvementin sustainability.

When the recycle stream is a polycondensation or addition polymertextile or fabric, or fibers, the material typically originates aspost-industrial off-grade or scrap, and can contain dyes and othercontaminants. Post industrial off-grade might originate from incorrectlydyed fabric or incorrectly woven textiles. Post industrial scrap canoriginate from leftover fabric that results from cutting fabric duringthe manufacture of clothing, carpet, furniture, shoes, curtains, andother textile based articles that use polycondensation or additionpolymer textiles or fabrics. Post consumer recycling of polycondensationor addition polymer textiles or fabrics can occur by utilizing worn-outclothing from apparel and uniform manufacturers and retailers as well asgovernment agencies, hospitals and clinics, schools, sports clubs, andother entities.

The thermoplastic polyester and glycol are heated, optionally in thepresence of a catalyst, to give a digested intermediate. The digestedintermediate will commonly be a mixture of glycol reactant, glycol(s)generated from the thermoplastic polyester, terephthalate oligomers, andother glycolysis products. For example, when PET or rPET is thethermoplastic polyester, the digested intermediate will include amixture of glycol reactant, ethylene glycol (generated from the PET orrPET), bis(2-hydroxyalkyl) terephthalate (“BHAT”), higher PET oligomers,and other glycolysis products. Similar digested mixtures in variousforms have been made and characterized previously (see, e.g., D. Paszunet al., Ind. Eng. Chem. Res. 36 (1997) 1373 and N. Ikladious, J. Elast.Plast. 32 (2000) 140). Heating is advantageously performed attemperatures within the range of 80° C. to 260° C., preferably 130° C.to 240° C., more preferably 150° C. to 230° C., and most preferably 160°C. to 220° C.

More specifically, in the context of the present invention, glycolysisrefers to the reaction of the hydroxyl group of a digested aromaticpolyacid source, e.g., a thermoplastic polyester intermediate with adigestible polymer in a manner to reduce the molecular weight of thedigestible polymer thereby providing a polyol that is liquid attemperatures between 20° C. and 120° C.

In one aspect, when the thermoplastic polyester is polyethyleneterephthalate, the digested intermediate comprises a glycol or mixtureof glycols and a terephthalate component. The glycols and terephthalatecomponents must be digested via a transesterification reaction and thisdigestion reaction is performed by heating the thermoplastic polyester,glycol(s), and any catalyst at least until the mixture liquefies andparticles of the thermoplastic polyester are no longer apparent at thetemperature of reaction. Reaction times range from about 30 minutes toabout 16 hours, more typically 1 to 10 hours, even more typically 3 to 8hours, and will depend on the reaction temperature, source of thethermoplastic polyester, the particular glycol reactant used, mixingrate, desired degree of depolymerization, and other factors that arewithin the skilled person's discretion.

The molar ratio of glycol to aromatic polyacid source is at least 0.8,preferably 2.0 to 6.0, more preferably 2.5 to 4.5. When theglycol/aromatic polyester source molar ratio is below about 2.0, theproducts are often solids at room temperature or too viscous to bepractical for use as conventional polyols for polyurethane applications,however, for the purpose of digesting digestible polymers at elevatedtemperatures, glycol to thermoplastic polyester ratios between 0.8 and2.0 are acceptable. On the other hand, when the glycol/aromaticpolyester source molar ratio is greater than about 6, the hydroxylnumbers of the resulting digested digestible polymer-based polyols tendto exceed the practical upper limit of about 800 mg KOH/g.

In a second reaction step, the digested intermediate described above isreacted with a digestible polymer to give the inventive polyesterpolyol.

The reaction between the digested intermediate and the digestiblepolymer is performed under conditions effective to promote reactionbetween one or more functional groups of the digestible polymer andhydroxyl groups present in the digested intermediate.

The weight percent of digestible polymer in the resulting polyesterproduct after digestion is from 1% to 75%, preferably from 3% to 60%,most preferably from about 5% to about 45%.

As long as some digestible polymer is used to make the polyol, one ormore other digestible polymers can also be included. Mixtures ofdigestible polymers can be used.

In another aspect, the polyester polyol is made in a single step, or onepot reaction, by reacting the aromatic polyacid source, glycol, anddigestible polymer under conditions effective to produce the polyol. Aswith polyols made using the two-step process, the weight percent ofdigestible polymer in the resulting polyester product after digestion isfrom 1% to 75%, preferably from 3% to 60%, most preferably from 5% to45%, the molar ratio of glycol to aromatic polyester source is at least0.8, and the resulting polyol has a hydroxyl number within the range of10 to 800 mg KOH/g. When the single-step process is used, it ispreferred to utilize a condensation system that returns glycols to thereaction vessel while allowing removal of water, as removal of too muchglycol can result in cloudy or opaque polyols. Examples III and IX belowillustrates the single-step process.

The inventive polyester polyols have hydroxyl numbers within the rangeof 10 to 800 mg KOH/g, preferably 25 to 500 mg KOH/g, more preferably 35to 400 mg KOH/g, and even more preferably 50 to 400 mg KOH/g. Hydroxylnumber can be measured by any accepted method for such a determination,including, e.g., ASTM E-222 (“Standard Test Methods for Hydroxyl GroupsUsing Acetic Anhydride Acetylation”).

The inventive polyols preferably have average hydroxyl functionalities(i.e., the average number of —OH groups per molecule) within the rangeof 1.5 to 5.0, more preferably 1.8 to 4.5, and most preferably 2.0 to4.0.

The inventive polyols are flowable liquids at temperatures between 20°C. and 125° C. Preferably, the polyols have viscosities measured atbetween 25° C. and 125° C. of less than about 20,000 cP. In someembodiments, the polyols have a viscosity at 25° C. less than about20,000 cP. In other embodiments, the polyols have a viscosity at 25° C.less than about 10,000 cP. In yet other embodiments, the polyols have aviscosity at 125° C. less than about 5000 cP. However, polyols outsidethese viscosity ranges can also be useful.

Viscosity can be determined by any industry-accepted method. It isconvenient to use, for instance, a Brookfield viscometer (such as aBrookfield DV-III Ultra rheometer) fitted with an appropriate spindle,and to measure a sample at several different torque settings to ensurean adequate confidence level in the measurements.

The polyols preferably have low acid numbers. Urethane manufacturerswill often require that a polyol have an acid number below a particularspecification. Low acid numbers can be ensured by driving thecondensation step (with digestible polymer) to the desired level ofcompletion or by adding an acid scavenger (e.g., Cardura™ E10P glycidylester manufactured by Momentive) at the conclusion of the condensationstep. Preferably, the polyols have an acid number less than 30 mg KOH/g,more preferably less than 10 mg KOH/g, and most preferably less than 5mg KOH/g. As suggested above, it is acceptable practice to adjust acidnumbers if necessary for a particular application with an acid scavengersuch as, for example, an epoxide derivative, and this treatment can beperformed by the manufacturer, distributor, or end user.

In the case of polyester polyols prepared using PU or PIR digestiblepolymers, small amounts of toluene diamine (TDA), methylene diphenylamine (MDA) or polymeric methylene diphenyl amine (PMDA) may be formed.As these substances are hazardous materials, it is desirable to reduceor eliminate their presence in the resulting polyester polyols. It isbelieved that this may be accomplished by introducing small amounts ofan amine scavenger such as, for example, an alkylene oxide, a glycidylether, an epoxy-derivative such as epoxidized soybean oil, an isocyanateor polyisocyanate derivative into the resulting polyester polyolconcurrent with heating and stirring to achieve reaction between theTDA, PMDA or MDA an the amine scavenger, thereby reducing the content ofthese hazardous substances in the polyester polyols derived from PU andPIR digestible polymers.

An advantage of the polyester polyols is their reduced reliance on bio-or petrochemical sources for raw material. Preferably, the polyolsinclude greater than 10 wt. %, more preferably greater than 25 wt. %,most preferably greater than 50 wt. % of recycle content. A preferredrange for the recycle content is 25 to 99.9 wt. %. By “recycle content,”we mean the combined amounts of recycled thermoplastic polyester and anyrecycled glycol or digestible polymer. Some glycols, such as propyleneglycol or ethylene glycol, are available as recovered or recycledmaterials. For instance, propylene glycol is used in deicing fluids, andafter use, it can be recovered, purified, and reused. Additionally,recycled ethylene glycol may be obtained from recovered engineantifreeze or engine coolant. Preferably, the digestible polymer isprepared or obtained from renewable resources or post-consumer orpost-industrial recycled sources. Recycle content can be calculated, forinstance, by combining the masses of recycled thermoplastic polyesterand any recycled glycol or recycled digestible polymer, dividing thissum by the total mass of reactants (glycols, thermoplastic polyester,and digestible polymer), and then multiplying the result by 100.

A desirable polyol attribute is the absence of settling, particularlyupon prolonged storage. When settling is substantial, the polyol mighthave to be filtered, stirred, stirred with heating or otherwise treatedto remove or redissolve the solids content; this is preferably avoided.Preferred inventive polyols exhibit no settling or only a slight degreeof settling, and more preferred polyols exhibit no evidence of settling.

In a specific aspect, the invention relates to a process whichcomprises: (a) heating virgin PET, recycled PET, or a mixture thereofwith propylene glycol in the presence of a zinc or titanium catalyst togive a digested intermediate; and (b) condensing the intermediate with adigestible polymer to give the polyester polyol; wherein the weightpercent of digestible polymer in the resulting polyester product afterdigestion is from 1% to 75%, preferably from 3% to 60%, most preferablyfrom about 5% to about 45%, the molar ratio of glycol to PET is withinthe range of 2.5 to 4.5, and the polyol has a hydroxyl number within therange of 25 to 500 mg KOH/g, a viscosity less than 20,000 cP between 25°C. and 90° C., and a recycle content as defined herein greater than 25wt. %.

Products Prepared from Polyols

The inventive polyester polyols can be used to formulate a wide varietyof polyurethane products. By adjusting the proportion of digestiblepolymer used, a desired degree of polyol hydrophobicity can be “dialedin.” The ability to control hydrophobicity is particularly valuable inthe coatings industry. The polyols can be used for cellular,microcellular, and non-cellular applications including flexible foams,rigid foams (including polyisocyanurate foams), urethane dispersions,coatings, powder coatings, adhesives, sealants, and elastomers. Theresulting polyurethanes are potentially useful for automotive andtransportation applications, building and construction products, marineproducts, packaging foam, flexible slabstock foam, carpet backing,appliance insulation, cast elastomers and moldings, footwear, biomedicaldevices, and other applications.

Further, the inventive polyester polyols may be derivatized to formmono-, di- and polyacrylates via esterification or transesterificationwith acrylic acid or methacrylic acid-derived raw materials. Examples of(meth)acrylation raw materials suitable for forming (meth)acrylatederivatives of the inventive polyester polyols include acryloylchloride, methacryloyl chloride, methacrylic acid, acrylic acid, methylacrylate, methyl methacrylate, and the like, or mixtures thereof. Such(meth)acrylate-derivatized inventive polyester polyols are useful forradiation or UV-cure coating formulations or applications. Isocyanateprepolymers of the inventive polyester polyols may be derivatized toform urethane (meth)acrylates via reaction with hydroxyethyl(meth)acrylate. The resulting urethane acrylates may also be used inradiation or UV-cure coating formulations or applications.

In a particular aspect, the invention relates to aqueous polyurethanedispersions made from the inventive polyester polyols. We found that thedigestible polymer modified polyols are readily formulated into aqueouspolyurethane dispersions having a desirable balance of properties,including high solids and low viscosities, and a low tendency to settle.Numerous ways to formulate aqueous polyurethane dispersions are knownand suitable for use. Preferably, the polyurethane dispersion is made byemulsifying an isocyanate-terminated prepolymer in water with the aid ofan emulsifiying agent. Water, a water-soluble polyamine chain extender,or a combination thereof may be used to react with the emulsifiedprepolymer. The prepolymer is preferably made by reacting an inventivepolyester polyol, a hydroxy-functional emulsifier, one or more auxiliarypolyols, and one or more polyisocyanates. The aqueous polyurethanedispersions are preferably used to formulate water-borne coatings,adhesives, sealants, elastomers, and similar urethane products, and theyare particularly valuable for reducing reliance on solvents. Forinstance, the dispersions can be used to formulate low- or zero-VOCcompositions.

Polyisocyanates suitable for use in making the prepolymers are wellknown; they include aromatic, aliphatic, and cycloaliphaticpolyisocyanates. Examples include toluene diisocyanates (TDIs), MDIs,polymeric MDIs, naphthalene diisocyanates (NDIs), hydrogenated MDIs,trimethyl- or tetramethylhexamethylene diisocyanates (TMDIs),hexamethylene diisocyanate (HDI), isophorone diisocyanates (IPDIs),cyclohexane diisocyanates (CHDIs), xylylene diisocyanates (XDI),hydrogenated XDIs, and the like. Aliphatic diisocyanates, such ashexamethylene diisocyanate and isophorone diisocyanates are particularlypreferred.

Auxiliary polyols suitable for use are also well known. They includepolyether polyols, aliphatic polyester polyols, aromatic polyesterpolyols, polycarbonate polyols, glycols, and the like. Preferredauxiliary polyols have average hydroxyl functionalities within the rangeof 2 to 6, preferably 2 to 3, and number average molecular weightswithin the range of 500 to 10,000, preferably 1,000 to 8,000. Preferredpolyester polyols are condensation products of aromatic or aliphaticdiacids and diols or triols (e.g., ethylene glycol, propylene glycol,2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 1,4-butanediol,neopentyl glycol, glycerin, trimethylolpropane,1,4-cyclohexanedimethanol, bisphenol A ethoxylates), especially diols.

A hydroxy-functional emulsifier is also used to make the polyurethanedispersions. The role of this component is to impartwater-dispersibility to the prepolymer, usually upon its combinationwith water and a neutralizing agent, such as an acid or base reactant.Thus, in one aspect, the hydroxy-functional emulsifier is anacid-functional diol such as dimethylolpropionic acid (DMPA) ordimethylolbutanoic acid (DMBA). The acid functionality in the resultingprepolymer allows for neutralization with an amine or other basicreactant to generate a water-dispersible urethane. Thehydroxy-functional emulsifier can also be an amine, such asN-methyldiethanolamine. Neutralization of the resulting prepolymer withan acidic reagent renders it water dispersible. In other aspects, thehydroxy-functional emulsifier is nonionic, e.g., a polyethylene glycolmonomethyl ether. In another aspect, the hydroxy-functional emulsifiermay be a monol- or diol-functionalized poly(ethylene oxide), such as forexample Ymer™ N120 dispersing monomer (product of Perstorp),polyethylene glycols, or the methyl ether of polyethylene glycol.Additionally, non-reactive, so-called “external emulsifiers,” such asthe triethanolamine salt of dodecylbenzene sulfonic acid, may beincluded in the aqueous phase to assist in the emulsification andstabilization of the prepolymer and resulting polyurethane dispersion.

In certain aspects, a chain terminator may be used to control themolecular weight of polyurethane polymer contained within the aqueouspolyurethane dispersion. Monofunctional compounds, such as thosecontaining hydroxyl, amino, and thio groups that have a single activehydrogen-containing group, are suitable chain terminators. Examplesinclude alcohols, amines, thiols, and the like, especially primary andsecondary aliphatic amines.

Chain extenders can also be included in making the polyurethanedispersion. In some aspects, the chain extender is added in an amountsufficient to react 5 to 105 mole % of free NCO groups present. Suitablechain extenders contain at least two functional groups that are capableof reacting with isocyanates, e.g., hydroxyl, thio, or amino groups inany combination. Suitable chain extenders include, for example, diols(ethylene glycol, propylene glycol, diethylene glycol, neopentyl glycol,1,4-butanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol,1,4-cyclohexanedimethanol, and the like), di- and polyamines(ethylenediamine, diethylenetriamine, Jeffamine® T-403, Jeffamine®D-230, Jeffamine® ED-2001, Jeffamine® ED-600, Jeffamine® ED-900,1,6-hexamethylenediamine, butylenediamine, hydrazine, piperazine,N-hydroxyethyl ethylenediamine) alkanolamines (ethanolamine,diethanolamine, N-methyl diethanolamine, and the like), dithiols, andthe like. Diol chain extenders are preferably added during thepreparation of the prepolymer, and prior to emulsification in water.

For more examples of suitable approaches for preparing aqueouspolyurethane dispersions, see U.S. Pat. Nos. 5,155,163; 5,608,000;5,763,526; 6,339,125; 6,635,723, 7,045,573; and 7,342,068, the teachingsof which are incorporated herein by reference.

Coatings

The polyester polyols of the present invention are useful for makingcoatings. A coating is a covering that is applied to the surface of anobject, which usually referred to as the substrate. The coatingstypically comprise from about 1% to about 95%, by weight of thepolyester polyol, preferably from about 2% to about 90% by weight of thepolyester polyol, and more preferably from about 5% to about 80% byweight of the polyester polyol. The optimum weight percentage of thepolyester polyol can be determined by one of skill in the art to obtainthe desired property of the coating both before and after application tothe substrate. Both liquid coatings and powder coatings can be made withthe polyols of the present invention. Examples of liquid coatingsinclude polyurethane coatings. These liquid coatings can includeadditional components such as catalysts, flow and leveling agents,surface modifying additives, wetting agents, dispersing agents,foam-control agents, solvents, crosslinking additives, co-blended resinsto modify properties, pigments and colorants, and degassing agents.

Powder coatings provide an important alternative to liquid coatings.These coatings can be prepared from resins, pigments, and additives. Thepowder is applied to a substrate, usually metal, and fused to form acontinuous film by baking the coated metal, or by applying the powdercoating to a heated substrate. The powder coatings typically have aglass transition temperature, T_(g), greater than or equal to 45° C.,preferably greater than or equal to 50° C., and more preferably greaterthan or equal to 55° C. The powder coatings also typically have amelting point greater than or equal to 45° C., preferably greater thanor equal to 50° C., and more preferably greater than or equal to 55° C.The glass transition temperature and the melting point of the powdercoating can be adjusted by the selection of the polyester polyol orpolyols incorporated, as well as the weight percentage of the polyol orpolyols in the coating. It is highly desirable to adjust the glasstransition temperature and melting point such that the powder coatingremains as a free flowing powder at room temperature and elevatedstorage conditions, such as for example in a hot warehouse, but alsoreadily melts to form a uniform coating on a substrate that has eitherbeen preheated before application of the powder coating or that issubsequently baked after application of the powder coating. While it isimportant to maintain a high enough glass transition temperature andmelt temperature to prevent sintering, it is desirable to simultaneouslytune the powder coating such that the optimal melt flow and crosslinkingtemperature is as low as possible, which results in a lower, narrowerprocess window for films. This lower temperature is advantageous from anenergy savings standpoint to the applicator. Additives are an importantingredient in the formulation of powder coatings. For the most part,additives perform the same functions in powder coatings as in liquidcoatings. With the exception of wetting, dispersing and foam-controlagents, many of the same additives used in liquid coatings are also usedin powders. The powder coatings can comprise additional components suchas crosslinking agents, flow control agents, degassing agents,catalysts, and pigmenting materials. The powder coatings can be appliedto a metal substrate using conventional techniques known in the art suchas electrostatic spraying. The metal substrate can either be preheatedbefore application of the powder coating or baked after the applicationof the powder coating to thermally set the coating.

See U.S. Pat. No. 5,637,654, to Panandiker et al, issued Jun. 10, 1997;U.S. Pat. No. 4,197,353, to Tobias et al, issued Apr. 8, 1980; PCTPatent Application No. WO 2011/138432 A1, to DSM IP Assets, B.V.,published Nov. 10, 2011; and “Organic Coatings Science and Technology”,3rd Ed., Wiley, 2007 Z. Wicks, Jr., F. Jones, S. P. Pappas, D. A. Wicks,Chapter 28.

EXAMPLES

The following examples further describe and demonstrate embodimentswithin the scope of the present invention. The Examples are given solelyfor purpose of illustration and are not to be construed as limitationsof the present invention, as many variations thereof are possiblewithout departing from the spirit and scope of the invention.

“Recycle content” as used herein (wt. %) is determined by combining themasses of recycled glycol, recycled aromatic polyacid source, recycledhydrophobe, and recycled digestible polymer, and dividing this sum bythe total mass of reactants, and then multiplying the result by 100.

Hydroxyl numbers and acid numbers are determined by standard methods(ASTM E-222 and ASTM D3339, respectively). Viscosities are measured at25° C. using a Brookfield DV-III Ultra rheometer with spindle #31 at25%, 50%, and 75% torque, with 50% torque being the usual torquesetting. Alternatively, depending on the viscosity of the sample,viscosities can also be measured at other temperatures, including up toabout 50° C. or higher. Also, viscosities can be determined on dilutedsamples. Color, clarity, and degree of settling are evaluated visually.

Examples I-VII provide procedures for carrying out the indicateddigestion process on an aromatic polyacid source to produce a digestedintermediate which can be utilized for further digesting the variousdigestible polymers of the present invention. Examples VIII-XXV provideprocedures for carrying out the further digestion of various digestiblepolymers. Example XXVI provides a procedure for making polyurethanecoatings from the polyols. Example XXVII provides a procedure for makingpowder coatings from the polyols. Examples XXVIII and XXIX provideprocedures for making rigid polyisocyanurate foams. Table 1 summarizesphysical characteristics data for the digestion product from variousaromatic polyacid sources. Table 2 summarizes physical characteristicsdata for the digestion products of various digestible polymers. Table 3summarizes physical characteristics data on polyurethane coatings madefrom the polyester polyols from the digestible polymers of the presentinvention.

Example I Preparation of Digested Intermediate from an Aromatic PolyacidSource (Recycled PET)

The following relative amounts of materials were used—(1.0 mole rPET/2.8mole PG/0.46 mole dimer fatty acid). A 5 liter reactor equipped with anoverhead mixer, condenser, heating mantle, thermocouple, and nitrogeninlet was charged with titanium tetrabutoxide (0.1% by wt.), recycledpolyethylene terephthalate pellets (960 g, 5 moles), and propyleneglycol (1065.2 g, 14 moles). The mixture was heated with stirring toabout 130° C. Stirring was then set to 60 rpm, and heating continueduntil the reactor contents reached 200° C. The mixture was heated untilno particles of recycled PET remained (about 4 hr). When the digestionreaction was considered complete, the mixture was cooled to about 100°C. Dimer fatty acid (Croda Pripol™ 1017, 1311.7 g, 2.3 moles) was added,while the mixing rate was increased to 200 rpm. When the addition wascomplete, a Dean-Stark trap was introduced between the reactor andcondenser, the mixture was then heated to 170° C. The temperature wasslowly increased over time to 185° C. depending on how fast water wascollected in the Dean Stark trap. Water generated in the condensationreaction was removed until roughly the theoretical amount was removed.When the reaction was complete, the digested intermediate was allowed tocool to 100° C. and then decanted from the reactor. Any residual solidswere removed by filtration through cheesecloth. The resultingtransparent amber digested intermediate had an OHV (hydroxyl value) of380 mg KOH/g of sample and a viscosity at 25° C. of 3097 cP(centipoise). See Acid Source Example 1 in Table 1.

Example II Preparation of Digested Intermediate from an AromaticPolyacid Source (Recycled PET Carpet)

A 2000 mL resin kettle equipped with an overhead mixer, Vigreux column,short path condenser head with distillation collection flask, heatingmantle, thermocouple, and nitrogen inlet was charged with 152.80 g ofrecycled propylene glycol, 142.80 g of recycled PET polyester carpetincluding polyolefin backing, calcium carbonate filler, and latexadhesive, assuming an approximate PET composition of 90% of the carpet,and 0.58 g titanium tetrabutoxide (˜0.1% by wt.) and heated with astirring rate of 150 RPM and nitrogen flow at 0.3SCFH to 200° C. for 20hours. After about 5 hours, the recycled PET polyester textile hadcompletely dissolved and appeared to be completely digested. The mixturewas heated overnight to ensure no particles of recycled PET carpetremained. The mixture was then cooled to about 100° C. 190.88 g of DimerFatty Acid (Croda Pripol 1017) was added, while the mixing rate wasincreased to 350 rpm. When the addition was complete the mixture wasthen heated to 200° C. and nitrogen was increased to 1.0SCFH. Watergenerated in the condensation reaction was collected in the distillationflask until roughly the theoretical amount was removed. When thereaction was complete, the reactor was allowed to cool to 100° C. andthen poured into a jar. Undigested polyolefin backing was removed byforceps and the mixture of polyol with calcium carbonate was run througha glass fritted disc filter size ‘F’ (<5 μm) at about 80° C. Theresulting transparent dark amber polyol had an OHV (hydroxyl value) of352.0 mg KOH/g of sample and a viscosity at 25° C. of 3000 cP(centipoise). See Acid Source Example 2 in Table 1.

Example III Preparation of Digested Intermediate from an AromaticPolyacid Source (Recycled PTT Carpet)

A 2000 mL resin kettle equipped with an overhead mixer, Vigreux column,short path condenser head with distillation collection flask, heatingmantle, thermocouple, and nitrogen inlet was charged with 149.47 g ofrecycled propylene glycol, 150.03 g of recycled PTT polyester carpetincluding polyolefin backing, calcium carbonate filler, and latexadhesive, assuming an approximate PTT composition of 90% of the carpet,and 0.58 g titanium tetrabutoxide (˜0.1% by wt.) and heated with astirring rate of 150 RPM and nitrogen flow at 0.3SCFH to 200° C. for 20hours. After about 5 hours, the recycled PTT polyester textile hadcompletely dissolved and appeared to be completely digested. The mixturewas heated overnight to ensure no particles of recycled PTT carpetremained. The mixture was then cooled to about 100° C. 186.72 g of DimerFatty Acid (Croda Pripol 1017) was added, while the mixing rate wasincreased to 350 rpm. When the addition was complete the mixture wasthen heated to 200° C. and nitrogen was increased to 1.0 SCFH. Watergenerated in the condensation reaction was collected in the distillationflask until roughly the theoretical amount was removed. When thereaction was complete, the reactor was allowed to cool to 100° C. andthen poured into a jar. Undigested polyolefin backing was removed byforceps and the mixture of polyol with calcium carbonate was run througha glass fritted disc filter size ‘F’ (<5 μm) at about 80° C. Theresulting transparent dark amber polyol had an OHV (hydroxyl value) of371.1 mg KOH/g of sample and a viscosity at 25° C. of 2307 cP(centipoise). See Acid Source Example 3 in Table 1.

Example IV Preparation of Digested Intermediate from an AromaticPolyacid Source (Recycled PET Textile)

A 500 mL reactor equipped with an overhead mixer, Vigreux column, shortpath condenser head with distillation collection flask, heating mantle,thermocouple, and nitrogen inlet was charged with 97.91 g of recycledpropylene glycol, 48.50 g of recycled PET polyester textile, and 0.30 gtitanium tetrabutoxide (˜0.1% by wt.) and heated with stirring to 200°C. for 6.0 hr. After about 5 hours, the recycled PET polyester textilehad completely dissolved and appeared to be completely digested. Themixture was heated until no particles of recycled PET polyester textileremained (about 6 hr). When the digestion reaction was consideredcomplete, the mixture was cooled to about 100° C. 65.80 g of Soybean Oiland 37.50 g of Phthalic Anhydride were added, while the mixing rate wasincreased to 200 rpm. When the addition was complete the mixture wasthen heated to 210° C. Water generated in the condensation reaction wascollected in the distillation flask until roughly the theoretical amountwas removed. When the reaction was complete, the digested intermediatewas allowed to cool to 100° C. and then decanted from the reactor. Anylarge residual solids were removed by filtration through cheesecloth.The resulting opaque dark purple-red polyol had an OHV (hydroxyl value)of 420.7 mg KOH/g of sample and a viscosity at 25° C. of 576 cP(centipoise). The final product was then further filtered through aBuchner funnel with filter paper to remove any residual solids that werenot removed by the cheesecloth. The resulting filtered transparent darkpurple-red polyol had an OHV (hydroxyl value) of 430.0 mg KOH/g ofsample and a viscosity at 25° C. of 588 cP (centipoise). See Acid SourceExample 4 (unfiltered) and Example 5 (filtered) in Table 1.

Example V Preparation of Digested Intermediate from Tritan Copolyester

A 1000 mL reactor equipped with an overhead mixer, Vigreux column, shortpath condenser head with distillation collection flask, heating mantle,thermocouple, and nitrogen inlet was charged with bio-based1,3-Propanediol (40.50% by weight), Tritan Copolyester flakecommercially available from Eastman (combination of dimethylterephthalate, 1,4-cyclohexanedimethanol, and2,2,4,4-tetramethyl-1,3-cyclobutanediol, seehttps://pubs.acs.org/cen/coverstory/89/8923cover4.html) (20.00% byweight), and titanium tetrabutoxide (˜0.1% by weight). The mixture washeated to 205° C. with a stirring rate of 220 rpm and nitrogen flow of˜0.5 SCFH for 6 hours. After about 4 hours, the Tritan Copolyester flakehad completely dissolved and appeared to be completely digested. Themixture was heated until no particles of Tritan Copolyester flakeremained (about 5 hr). The mixture was cooled to about 100° C. Bio-basedsuccinic acid (39.40% by weight) was added, while the mixing rate wasincreased to 350 rpm. When the addition was complete, the mixture wasthen heated to 205° C., and the nitrogen flow rate was increased to ˜1.0SCFH (standard cubic feet per hour). Water generated in the condensationreaction was collected in the distillation flask until roughly thetheoretical amount was removed. When the reaction was complete asdetermined by a low acid value (less than 5 mgKOH/g), the digestedintermediate was allowed to cool to 100° C. and then decanted from thereactor. Any large residual solids were removed by filtration throughcheesecloth. The resulting opaque grey polyol had an OHV (hydroxylvalue) of 239 mg KOH/g of sample and a viscosity at 25° C. of 5,800 cP(centipoise). See Acid Source Example 8 in Table 1.

Example VI Preparation of Digested Intermediate from Polymer ofCyclohexanedimethanol Terephthalic Acid (PCTA)—1

A 1000 mL reactor equipped with an overhead mixer, Vigreux column, shortpath condenser head with distillation collection flask, heating mantle,thermocouple, and nitrogen inlet was charged with recycled propyleneglycol (9.70% by weight), bio-based glycerol (1.75% by weight),neopentyl glycol (16.39% by weight), recycled PCTA flake commerciallyavailable from Eastman (38.80% by weight), and monobutyltin tinhydroxide oxide (˜0.15% by weight). The mixture was heated to 200° C.with a stirring rate of 150 rpm and nitrogen flow of ˜0.5 SCFH for 4hours. After about 3 hours, the recycled PCTA flake had completelydissolved and appeared to be completely digested. The mixture was heateduntil no particles of recycled PCTA flake remained (about 4 hr). Themixture was cooled to about 100° C. Bio-based succinic acid (39.40% byweight) and isopthalic acid (8.68% by weight) were added, while themixing rate was increased to 350 rpm. When the addition was complete,the mixture was then heated to 200° C., and the nitrogen flow rate wasincreased to ˜1.0 SCFH. Water generated in the condensation reaction wascollected in the distillation flask until roughly the theoretical amountwas removed. When the reaction was complete as determined by a low acidvalue (less than 5 mgKOH/g), the digested intermediate was cut withn-Butyl acetate (targeted 80% solids). The intermediate polyol andsolvent was mixed for around 1.5 hrs at 120° C. and was allowed to coolto 100° C. and then decanted from the reactor. Any large residual solidswere removed by filtration through cheesecloth. The resultingtranslucent grey polyol had an OHV (hydroxyl value) of 36 mg KOH/g ofsample and a viscosity at 50° C. of 24,000 cP (centipoise) at a dilutionof 81.57% by weight solids in n-Butyl acetate. See Acid Source Example 9in Table 1.

Example VII Preparation of Digested Intermediate from Polymer ofCyclohexanedimethanol Terephthalic Acid (PCTA)—2

A 500 mL reactor equipped with an overhead mixer, Vigreux column, shortpath condenser head with distillation collection flask, heating mantle,thermocouple, and nitrogen inlet was charged with Cyclohexanedimethanol(50.00% by weight), recycled PCTA flake commercially available fromEastman (30.00% by weight), and titanium tetrabutoxide (˜0.1% byweight). The mixture was heated to 200° C. with a stirring rate of 150rpm and nitrogen flow of ˜0.5 SCFH for 3 hours. After about 2 hours, therecycled PCTA flake had completely dissolved and appeared to becompletely digested. The mixture was heated until no particles ofrecycled PCTA flake remained (about 3 hr). The mixture was cooled toabout 100° C. Dimer fatty acid Priol 1017 (10.00% by weight)commercially available from Croda and terephthalic acid (10.00% byweight) were added, while the mixing rate was increased to 350 rpm. Whenthe addition was complete, the mixture was then heated to 205° C., andthe nitrogen flow rate was increased to ˜1.0 SCFH. Water generated inthe condensation reaction was collected in the distillation flask untilroughly the theoretical amount was removed. When the reaction wascomplete as determined by a low acid value (less than 5 mgKOH/g), thedigested intermediate was allowed to cool to 100° C. and then decantedfrom the reactor. Any large residual solids were removed by filtrationthrough cheesecloth. The resulting opaque grey polyol had an OHV(hydroxyl value) of 321.7 mg KOH/g of sample. See Acid Source Example 10in Table 1.

Example VIII Digestion of Recycled Polyurethane Foam

A 500 mL reactor equipped with an overhead mixer, condenser, heatingmantle, thermocouple, and nitrogen inlet is charged with 232.14 g of thedigested intermediate product described above from Example I and 30.41 gof recycled flexible polyurethane foam (Carex Health Brands knee pillowmemory foam). The foam was cut to form pieces approximately 0.5 inchesin diameter prior to introduction in the reactor. Stirring with heatingand nitrogen purge was initiated until a temperature of 150° C. wasachieved. After approximately 2 hours, the foam had completelydissolved. The temperature was raised to 180° C. for another 30 minutesand then heating was turned off. The mixture was poured out of thereactor at a temperature of 100° C. The resulting polyester polyol hadan OHV of 321 mg KOH/g of sample, a viscosity of 8098 cP at 25° C. Uponstoring the polyol for several days, no settling was observed in thedark green, opaque, but flowable product.

The 4,4′-methylenedianiline (MDA) content of this polyol was determinedto be 4405 ppm initially by gas chromatography. A small sample of thepolyol was heated to 100° C., and treated with an equimolar (based onMDA content) amount of Cardura™ E10P with stirring for about 2 hours.Cardura E10P is the glycidyl ester of a synthetic saturatedmonocarboxylic acid of highly branched C10 isomers. The resulting MDAcontent was reduced to 2075 ppm as measured by gas chromatography,indicating that the MDA content in these recycled PU foam polyols can bereduced by the utilization of amine scavengers, though optimization ofthe conditions and perhaps the type of scavenger appear to warrantfurther study.

Example IX Digestion of Goose Down

A 500 mL reactor equipped with an overhead mixer, condenser, heatingmantle, thermocouple, and nitrogen inlet is charged with 144.1 g ofrPET, 159.9 g of recycled propylene glycol, 0.5 g of titaniumtetrabutoxide (0.1% by wt.), and 28.28 g of goose down feathers. Thetemperature was raised to 186° C. with stirring. Reflux was observed andthe temperature was raised to 200° C. A Dean Stark trap was added tocollect the refluxing liquid. After about 3 hours, the goose down hadcompletely dissolved, and the reaction was cooled to 100° C., whereuponthe contents of the Dean Stark trap were added back into the reactionmixture and stirred to homogenize the mixture. One half of the reactorcontents (104.72 g) were poured into a bottle to permit hydrophobemodification of the second half. This dark brown polyester polyol(Polyol Example 22 in Table 2) yielded an acid value of 2.1 mg KOH/g, anOHV of 664.1, a viscosity of 2946 cP at 25° C. and no settling afterseveral days.

Dimer fatty acid (135.12 g, 0.345 mole) was added to the remainingpolyester polyol product and the temperature raised to 185° C. for 4hours, followed by further heating at between 180 and 200° C. foranother 10 hours. The resulting dark brown polyester polyol (PolyolExample 23 in Table 2) yielded an acid value of 2.8 mg KOH/g and an OHVof 336.4 g KOH/g, a viscosity of 7113 cP at 25° C. and had no settlingover the course of several days.

Example X Digestion of Poly(bisphenol A carbonate)

A 500 mL reactor equipped with an overhead mixer, condenser, heatingmantle, thermocouple, and nitrogen inlet was charged with 28.55 g ofpoly(bisphenol A carbonate) and 198.22 g of Stepanpol™ PS-2352(available from Stepan Company) and heated with stirring to 200° C. for5.5 hr. After about 3 hours, the poly(bisphenol A carbonate) hadcompletely dissolved and appeared to be completely digested. Theresulting pale orange, transparent polyester polyol (Polyol Example 38in Table 2) yielded an acid value of 7.4 mg KOH/g, an OHV of 220.0, aviscosity of 15207 cps at 25° C. and no settling after several days.

Example XI Digestion of Potato Starch

A 500 mL reactor equipped with an overhead mixer, condenser, heatingmantle, thermocouple, and nitrogen inlet is charged with 96.0 g of rPET,114.33 g of recycled propylene glycol, 0.25 g of titanium tetrabutoxide(0.1% by wt.), and 25.5 g of potato starch. The temperature was raisedto 185° C. for 2 hours with stirring. Reflux was observed and thetemperature was raised to 195° C. for another 3 hours. At this point theheat was turned off for the day, and the digestion, based on amount ofdissolved potato starch was approximately 85% complete. The next day,the heat was turned back on for another 2 hours to a temperature of 196°C. Although the reaction product was very dark brown, there was noevidence of undissolved potato starch. The reaction was cooled to 105°C. and p-toluene sulfonic acid (0.26 g) was added followed by raisingthe temperature to 150° C. for one hour. A Dean Stark trap was added tocollect refluxing liquid. The reaction mixture was then heated to 200°C. for about 30 minutes. At this point, only 0.22 mL of water werecollected, and the reaction mixture was quite dark. The reaction mixturewas then cooled to 50° C. and diethanol amine (0.20 g) added. Theproduct was allowed to stir at this temperature for another 30 minutesand then allowed to cool to room temperature. This dark brown polyesterpolyol (Polyol Example 34 in Table 2) yielded an acid value of 6.4 mgKOH/g, an OHV of 396.7, a viscosity of 5632 cP at 25° C. and no apparentsettling after several days.

Example XII Digestion of Goose Down

A 1 L reactor equipped with an overhead mixer, condenser, heatingmantle, thermocouple, and nitrogen inlet is charged with 351.1 g ofdiethylene glycol, followed by eleven additions of goose down at areaction temperature of 180-185° C., each averaging 26.04 g over thecourse of the next 23 hours. Prior to each addition, the reactionmixture was inspected visually prior to adding another aliquot of goosedown to insure that the previous addition had undergone full digestionand dissolution.

At this point, the polyester polyol was cooled to 121° C. and 299.3 g ofthe product were removed from the reactor. This dark brown polyesterpolyol (Polyol Example 24 in Table 1) yielded an acid value of 25.7 mgKOH/g, an OHV of 622.1, a viscosity of 3488 cP at 25° C. and no apparentsettling after several days at room temperature. A similar procedure wasused for (Polyol Example 27 in Table 2), except that the goose down wasadded together with the diethylene glycol in a single addition, followedby stirring at between 180 and 200° C.

A Dean Stark trap was connected to the reactor and ricinoleic acid (40%by wt. based on the remaining polyester polyol remaining in the reactor)was added. The contents were heated with stirring to 185° C. for 2.6hours. This dark brown polyester polyol (Polyol Example 25 in Table 2)yielded an acid value of 14.0 mg KOH/g, an OHV of 369.9, a viscosity of980.2 cP at 25° C. and no apparent settling after several days at roomtemperature.

Example XIII Digestion of Nylon-6,6 Carpet

A 500 mL reactor equipped with an overhead mixer, virgeux column, shortpath condenser head with distillation collection flask, heating mantle,thermocouple, and nitrogen inlet was charged with 76.21 g of recycledpropylene glycol, 50.19 g of recycled nylon-6,6 carpet, and 0.30 gtitanium tetrabutoxide (˜0.1% by wt.) and heated with stirring to 200°C. for 1.0 hr. After about 1 hour, it did not appear that the recyclednylon-6,6 carpet was digesting, the mixture was cooled to 100° C. and72.00 g of recycled diethylene glycol was added. The mixture was heatedagain to 200° C. until no particles of recycled nylon-6,6 carpetremained (about 6 hr). After about 6.0 hours, the recycled nylon-6,6carpet had completely dissolved and appeared to be completely digested.When the digestion reaction was considered complete, the mixture wascooled to about 100° C. 132.00 g of soybean oil and 72.13 g of phthalicanhydride were added, while the mixing rate was increased to 200 rpm.When the addition was complete the mixture was then heated to 210° C.Water generated in the condensation reaction was collected in thedistillation flask until roughly the theoretical amount was removed.When the reaction was complete, the digested intermediate was allowed tocool to 100° C. and then decanted from the reactor. The resulting polyolconsisted of two non-digestible phases and one polyol phase. The twonon-digestible phases was a grey solid chuck of polyolefin and latexadhesives, as well as grey calcium carbonate particulate residue thatsettled at the bottom. Any large residual solids (polyolefin and latexadhesive chuck) were removed by filtration through cheesecloth. Thefinal product was then further filtered through a Buchner funnel with afilter paper to remove any residual solids that were not removed by thecheesecloth (calcium carbonate particulate). The resulting filteredopaque brown polyol had an OHV (hydroxyl value) of 353.7 mg KOH/g ofsample and a viscosity at 25° C. of 601 cP (centipoise). See PolyolExample 40 in Table 2.

Example XIV Digestion of Chicken Feather Meal

A 500 mL reactor equipped with an overhead mixer, Vigreux column, shortpath condenser head with distillation collection flask, heating mantle,thermocouple, and nitrogen inlet was charged with 101.46 g of recycleddiethylene glycol, 27.95 g of chicken feather meal, and 0.30 g titaniumtetrabutoxide (˜0.1% by wt.) and heated with stirring to 210° C. for 3hr. After about 2 hours, the chicken feather meal had completelydissolved and appeared to be completely digested. The mixture was heateduntil no particles of chicken feather meal remained (about 2.5 hr). Whenthe digestion reaction was considered complete, the mixture was cooledto about 100° C. 98.00 g of soybean oil and 25.00 g of phthalicanhydride were added, while the mixing rate was increased to 200 rpm.When the addition was complete the mixture was then heated to 215° C.Water generated in the condensation reaction was collected in thedistillation flask until roughly the theoretical amount was removed.When the reaction was complete, the digested intermediate was allowed tocool to 100° C. and then decanted from the reactor. Any residualparticles were removed by filtration through cheesecloth. The resultingopaque dark black-brown polyol had an OHV (hydroxyl value) of 351.6 mgKOH/g of sample and a viscosity at 25° C. of 196.5 cP (centipoise).

Example XV Digestion of Corn Zein

A 5000 mL reactor equipped with an overhead mixer, Vigreux column, shortpath condenser head with distillation collection flask, heating mantle,thermocouple, and nitrogen inlet was charged with 1447.17 g of recycleddiethylene glycol and 298.50 g of corn zein and heated with stirring to40° C. for 2 hr. After about 2 hours, the corn zein had completelydissolved in the recycled diethylene glycol. When the corn zein hadcompletely dissolved in the recycled diethylene glycol, the mixture washeated to about 100° C. 1023.00 g of phthalic anhydride and 1.40 gtitanium tetrabutoxide (˜0.1% by wt.) were added, while the mixing ratewas increased to 200 rpm. When the addition was complete the mixture wasthen heated to 200° C. After about 2 hours, the mixture was heated toabout 210° C. Water generated in the condensation reaction was collectedin the distillation flask until roughly the theoretical amount wasremoved. Throughout the duration of the reaction, aliquots of thedigestion were taken to check hydroxyl and acid values. Low acid numberscan be ensured by driving the condensation step (with digestiblepolymer) to the desired level of completion or by adding an acidscavenger (e.g., Cardura™ E10P glycidyl ester manufactured by Momentive)at the conclusion of the condensation step. As suggested above, it isacceptable practice to adjust acid numbers if necessary for a particularapplication with an acid scavenger such as, for example, an epoxidederivative, and this treatment can be performed by the manufacturer,distributor, or end user. 40.00 g of Cardura™ E10P glycidyl ester acidscavenger was added to ensure a low acid value. In order to stay in atarget hydroxyl value range, the addition of recycled diethylene glycolis necessary. After about 12 hours, the mixture was cooled to about 100°C. 300.00 g of recycled diethylene glycol was added, while the mixingrate was increased to 200 rpm. When the addition was complete themixture was then heated to 200° C. When the reaction was complete asdetermined by a low acid value (less than 5), the digested intermediatewas allowed to cool to 100° C. and then decanted from the reactor. Anyresidual particulates were removed by filtration through cheesecloth.The resulting opaque dark black-brown polyol had an OHV (hydroxyl value)of 265.0 mg KOH/g of sample and a viscosity at 25° C. of 4045 cP(centipoise).

Example XVI Digestion of Soy Flour

A 500 mL reactor equipped with an overhead mixer, Vigreux column, shortpath condenser head with distillation collection flask, heating mantle,thermocouple, and nitrogen inlet was charged with 87.50 g of recycledpropylene glycol, 62.53 g of recycled polyethylene terephthalatepellets, 25.04 g of Soy flour, and 0.30 g titanium tetrabutoxide (˜0.1%by wt.) and heated with stirring to 205° C. for 1.0 hr. After about 5hours, the soy flour and recycled polyethylene terephthalate pellets hadcompletely dissolved and appeared to be completely digested. The mixturewas heated until no particles of soy flour and recycled polyethyleneterephthalate pellets remained (6 hr). When the digestion reaction wasconsidered complete, the mixture was cooled to about 100° C. 71.90 g ofsoybean oil was added, while the mixing rate was increased to 200 rpm.When the addition was complete the mixture was then heated to 210° C.Water generated in the condensation reaction was collected in thedistillation flask until roughly the theoretical amount was removed.When the reaction was complete, the digested intermediate was allowed tocool to 100° C. and then decanted from the reactor. Any residualparticulates were removed by filtration through cheesecloth. Theresulting opaque dark black-brown polyol had an OHV (hydroxyl value) of384.9 mg KOH/g of sample and a viscosity at 25° C. of 872.1 cP(centipoise).

Example XVII Digestion of Polysaccharide (Pectin)

A 500 mL reactor equipped with an overhead mixer, Vigreux column, shortpath condenser head with distillation collection flask, heating mantle,thermocouple, and nitrogen inlet was charged with the digestedintermediate product (76.5% by weight) as described above from Example Iand pectin (23.5% by weight). The mixture was heated to 210° C. with astirring rate of 150 rpm and nitrogen flow of ˜0.5 SCFH for 12 hours.Water generated in the condensation reaction was collected in thedistillation flask until roughly the theoretical amount was removed.When the reaction was complete as determined by a low acid value (lessthan 5 mgKOH/g), the digested intermediate was allowed to cool to 100°C. and then decanted from the reactor. Any large residual solids wereremoved by filtration through cheesecloth. Undigested pectin was removedby filtration through a glass fritted disc filter size ‘F’ (<5 μm) atabout 80° C. The resulting transparent dark brown polyol had an OHV(hydroxyl value) of 228.3 mg KOH/g of sample and a viscosity at 25° C.of 5,733 cP (centipoise). See, Polyol Example 41 in Table 2.

Example XVIII Digestion of Recycled Poly(Bisphenol A carbonate)—1

A 500 mL reactor equipped with an overhead mixer, Vigreux column, shortpath condenser head with distillation collection flask, heating mantle,thermocouple, and nitrogen inlet was charged with recycled propyleneglycol (17% by weight), recycled polyethylene terephthalate pellets (39%by weight), recycled poly(bisphenol A carbonate) pellets (9% by weight),bio-based BiOH® 5300 polyol (17% by weight) commercially available fromCargill, and titanium tetrabutoxide (˜0.1% by weight). The mixture washeated to 200° C. with a stirring rate of 150 rpm and nitrogen flow of˜0.5 SCFH for 6 hours. After about 5 hours, the recycled polyethyleneterephthalate and recycled poly(bisphenol A carbonate) pellets hadcompletely dissolved and appeared to be completely digested. The mixturewas heated until no particles of recycled polyethylene terephthalate andrecycled poly(bisphenol A carbonate) pellets remained (about 6 hr). Themixture was cooled to about 100° C. Bio-based succinic acid (17.9% byweight) was added, while the mixing rate was increased to 350 rpm. Whenthe addition was complete, the mixture was then heated to 205° C., andthe nitrogen flow rate was increased to ˜1.0 SCFH. Water generated inthe condensation reaction was collected in the distillation flask untilroughly the theoretical amount was removed. When the reaction wascomplete as determined by a low acid value (less than 5 mgKOH/g), thedigested intermediate was allowed to cool to 100° C. and then decantedfrom the reactor. Any large residual solids were removed by filtrationthrough cheesecloth. The resulting translucent dark amber polyol had anOHV (hydroxyl value) of 134.1 mg KOH/g of sample and a viscosity at 100°C. of 9,000 cP (centipoise). See, Polyol Example 42 in Table 2.

Example XIX Digestion of Recycled Poly(bisphenol A carbonate)—2

A 500 mL reactor equipped with an overhead mixer, Vigreux column, shortpath condenser head with distillation collection flask, heating mantle,thermocouple, and nitrogen inlet was charged with Stepanpol PN 110 (85%by weight) a neopentyl glycol-phthalic anhydride-based polyester polyolcommercially available from the Stepan Company, and recycledpoly(bisphenol A carbonate) pellets (15% by weight). The mixture washeated to 210° C. with a stirring rate of ˜50 rpm and nitrogen flow of˜0.8 SCFH for 1 hour. After about 1 hour, the recycled poly(bisphenol Acarbonate) pellets had completely dissolved and appeared to becompletely digested. The mixture stirring rate was then increased to˜150 rpm for 3 hours. The mixture was heated until no particles ofrecycled poly(bisphenol A carbonate) pellets remained (about 4 hr).Water generated in the condensation reaction was collected in thedistillation flask until roughly the theoretical amount was removed.When the reaction was complete as determined by a low acid value (lessthan 5 mgKOH/g), the digested intermediate was allowed to cool to 100°C. and then decanted from the reactor. Any large residual solids wereremoved by filtration through cheesecloth. The resulting opaque whitepolyol had an OHV (hydroxyl value) of 73.6 mg KOH/g of sample and aviscosity at 75° C. of 9,410 cP (centipoise). See, Polyol Example 43 inTable 2.

Example XX Digestion of Recycled Poly(bisphenol A carbonate)—3

Part A. Preparation of digested intermediate from recycled polyethyleneterephthalate pellets: A 500 mL reactor equipped with an overhead mixer,Vigreux column, short path condenser head with distillation collectionflask, heating mantle, thermocouple, and nitrogen inlet was charged withrecycled propylene glycol (15.48% by weight), recycled polyethyleneterephthalate pellets (49.95% by weight), trimethylolpropane (5.49% byweight), and butyltin hydroxide oxide hydrate (˜0.1% by weight). Themixture was heated to 200° C. with a stirring rate of 150 rpm andnitrogen flow of ˜0.5 SCFH for 7 hours. After about 5 hours, therecycled polyethylene terephthalate pellets had completely dissolved andappeared to be completely digested. The mixture was heated until noparticles of recycled polyethylene terephthalate pellets remained. Themixture was cooled to about 100° C. Bio-based succinic acid (17.9% byweight) and dimer fatty acid Priol 1017 (14.24% by weight) commerciallyavailable from Croda was added, while the mixing rate was increased to350 rpm. When the addition was complete, the mixture was then heated to200° C. with a stirring rate of 150 rpm and the nitrogen flow wasincreased to ˜1.0 SCFH. Water generated in the condensation reaction wascollected in the distillation flask until roughly the theoretical amountwas removed. When the reaction was complete as determined by a low acidvalue (less than 5 mgKOH/g), the digested intermediate was allowed tocool to 100° C. and then decanted from the reactor. Any large residualsolids were removed by filtration through cheesecloth. The resultingtransparent dark amber polyol had an OHV (hydroxyl value) of 103.7 mgKOH/g of sample and a viscosity at 100° C. of 6,035 cP (centipoise).

Part B: Digestion or recycled poly(bisphenol A carbonate): A 500 mLreactor equipped with an overhead mixer, Vigreux column, short pathcondenser head with distillation collection flask, heating mantle,thermocouple, and nitrogen inlet was charged with a previously preparedaromatic polyester polyol (see Part A, above) (65% by weight) andrecycled poly(bisphenol A carbonate) pellets (8% by weight). The mixturewas heated to 210° C. with a stirring rate of ˜50 rpm and nitrogen flowof ˜0.8 SCFH for 1 hour. After about 1 hour, the recycled poly(bisphenolA carbonate) pellets had completely dissolved and appeared to becompletely digested. The mixture stirring rate was then increased to˜150 rpm for 3 hours. The mixture was heated until no particles ofrecycled poly(bisphenol A carbonate) pellets remained (about 4 hr).Water generated in the condensation reaction was collected in thedistillation flask until roughly the theoretical amount was removed.When the reaction was complete as determined by a low acid value (lessthan 5 mgKOH/g), the digested intermediate was allowed to cool to 100°C. and then decanted from the reactor. Any large residual solids wereremoved by filtration through cheesecloth. The resulting translucentgreen polyol had an OHV (hydroxyl value) of 93.6 mg KOH/g of sample anda viscosity at 25° C. of 31,056 cP (centipoise), note that the polyolwas cut with xylene to around 79% solids to achieve this viscosityreading. See, Polyol Example 44 in Table 2.

Example XXI Digestion of Recycled Poly(bisphenol A carbonate)—4

A 500 mL reactor equipped with an overhead mixer, Vigreux column, shortpath condenser head with distillation collection flask, heating mantle,thermocouple, and nitrogen inlet was charged with a previously preparedaromatic polyester polyol [see digestion of recycled poly(bisphenol Acarbonate)—BP1000P-2.6A as described in the above Example XV] (65% byweight) and bio-based glycerol (5% by weight). The mixture was heated to210° C. with a stirring rate of ˜150 rpm and nitrogen flow of ˜0.8 SCFHfor 2 hours. The mixture was then cooled to about 100° C. and bio-basedlinoleic Acid (30% by weight) was added, while the mixing rate wasincreased to 350 rpm. When the addition was complete, the mixture wasthen heated to 210° C., and nitrogen was increased to ˜1.0 SCFH. Watergenerated in the condensation reaction was collected in the distillationflask until roughly the theoretical amount was removed. When thereaction was complete as determined by a low acid value (less than 5mgKOH/g), the digested intermediate was allowed to cool to 100° C.Recycled poly(bisphenol A carbonate) pellets (3.25% by weight) was thenadded while the mixing rate was increased to 350 rpm. When the additionwas complete the mixture was heated to 210° C. until no particles ofrecycled poly(bisphenol A carbonate) pellets remained (about 4 hr). Thedigested intermediate was allowed to cool to 100° C. and then decantedfrom the reactor. Any large residual solids were removed by filtrationthrough cheesecloth. The resulting transparent golden polyol had an OHV(hydroxyl value) of 91.2 mg KOH/g of sample and a viscosity at 50° C. of5,768 cP (centipoise). See, Polyol Example 45 in Table 2.

Example XXII Digestion of Recycled Poly(bisphenol A carbonate)—5

A 1000 mL reactor equipped with an overhead mixer, Vigreux column, shortpath condenser head with distillation collection flask, heating mantle,thermocouple, and nitrogen inlet was charged with recycled propyleneglycol (7.8% by weight), recycled polyethylene terephthalate pellets(31.2% by weight), recycled poly(bisphenol A carbonate) pellets (19.5%by weight), bio-based glycerol (1.4% by weight), neopentyl glycol (13.2%by weight), and butyltin hydroxide oxide hydrate (˜0.1% by weight). Themixture was heated to 200° C. with a stirring rate of 300 rpm andnitrogen flow of ˜0.3 SCFH for 6 hours. After about 5 hours, therecycled polyethylene terephthalate and recycled poly(bisphenol Acarbonate) pellets had completely dissolved and appeared to becompletely digested. The mixture was heated until no particles ofrecycled polyethylene terephthalate and recycled poly(bisphenol Acarbonate) pellets remained (about 6 hr). When the digestion reactionwas considered complete, the mixture was cooled to about 100° C.Bio-based succinic acid (19.8% by weight) and isophthalic acid (7% byweight) were added, while the mixing rate was increased to 300 rpm. Whenthe addition was complete, the mixture was then heated to 205° C., andnitrogen was increased to ˜1.0 SCFH. Water generated in the condensationreaction was collected in the distillation flask until roughly thetheoretical amount was removed. When the reaction was complete asdetermined by a low acid value (less than 5 mgKOH/g), the digestedintermediate was allowed to cool to 100° C. and then decanted from thereactor. Any large residual solids were removed by filtration throughcheesecloth. The resulting translucent green polyol had an OHV (hydroxylvalue) of 75.3 mg KOH/g of sample. See, Polyol Example 46 in Table 2.

Example XXIII Digestion of Recycled Poly(bisphenol A carbonate)—6

A 500 mL reactor equipped with an overhead mixer, Vigreux column, shortpath condenser head with distillation collection flask, heating mantle,thermocouple, and nitrogen inlet was charged with a previously preparedaromatic polyester polyol [Preparation of Digested Intermediate fromTritan Copolyester as described in the above Example V] (90.63% byweight) and recycled Poly(Bisphenol a carbonate) pellets (9.37% byweight). The mixture was heated to 205° C. with a stirring rate of ˜150rpm and nitrogen flow of ˜0.8 SCFH for 4 hours. After about 2 hours, therecycled Poly(Bisphenol a carbonate) pellets had completely dissolvedand appeared to be completely digested. The mixture was heated until noparticles of recycled Poly(Bisphenol a carbonate) pellets remained(about 4 hr). The digested intermediate was allowed to cool to 100° C.and then decanted from the reactor. Any large residual solids wereremoved by filtration through cheesecloth. The resulting transparentyellow-gold polyol had an OHV (hydroxyl value) of 202.1 mg KOH/g ofsample and a viscosity at 25° C. of 17,496 cP (centipoise). See, PolyolExample 47 in Table 2.

Example XXIV Digestion of Recycled Poly(bisphenol A carbonate)—7

A 500 mL reactor equipped with an overhead mixer, Vigreux column, shortpath condenser head with distillation collection flask, heating mantle,thermocouple, and nitrogen inlet was charged with a previously preparedaromatic polyester polyol [Preparation of Digested Intermediate fromPCTA as described in the above Example VI] (90.53% by weight) andrecycled Poly(Bisphenol a carbonate) pellets (9.47% by weight). Themixture was heated to 205° C. with a stirring rate of ˜150 rpm andnitrogen flow of ˜0.8 SCFH for 4 hours. After about 2 hours, therecycled Poly(Bisphenol a carbonate) pellets had completely dissolvedand appeared to be completely digested. The mixture was heated until noparticles of recycled Poly(Bisphenol a carbonate) pellets remained(about 4 hr) and then was cut with n-Butyl acetate (targeted 60%solids). The intermediate polyol and solvent was mixed for around 0.5hrs at 120° C. and was allowed to cool to 100° C. and then decanted fromthe reactor. Any large residual solids were removed by filtrationthrough cheesecloth. The resulting opaque green polyol had an OHV(hydroxyl value) of 36.4 KOH/g of sample. See, Polyol Example 48 inTable 2.

Example XXV Digestion of Recycled Poly(bisphenol A carbonate)—8

A 500 mL reactor equipped with an overhead mixer, Vigreux column, shortpath condenser head with distillation collection flask, heating mantle,thermocouple, and nitrogen inlet was charged with a previously preparedaromatic polyester polyol [Preparation of Digested Intermediate fromPCTA as described in the above Example VII] (90.96% by weight) andrecycled Poly(Bisphenol a carbonate) pellets (9.04% by weight). Themixture was heated to 205° C. with a stirring rate of ˜150 rpm andnitrogen flow of ˜0.8 SCFH for 4 hours. After about 2 hours, therecycled Poly(Bisphenol a carbonate) pellets had completely dissolvedand appeared to be completely digested. The mixture was heated until noparticles of recycled Poly(Bisphenol a carbonate) pellets remained(about 4 hr). The digested intermediate was allowed to cool to 100° C.and then decanted from the reactor. Any large residual solids wereremoved by filtration through cheesecloth. The opaque, light grey polyolhad an OHV (hydroxyl value) of 255.0 KOH/g of sample. See, PolyolExample 49 in Table 2.

Example XXVI Procedure for Preparing Polyurethane Coatings

The following is a procedure for making a two-component (“2 K”) coating.The polyester polyol (14.11g, 0.098 equiv.), 2-methyl-1,3-propanediol(0.7 g, 0.008 equiv.), and ethylene glycol (1.12 g, 0.037 equiv.) wereadded to an 250 mL beaker, at room temperature. Hexamethylenediisocyanate (8.97 g, 0.107 equiv.) and isophorone diisocyanate (5.08 g,0.023 equiv.) were then added to the beaker. The mixture was thendiluted to 50% by weight with 2-butanone. Mechanical mixing wasinitiated using a tri-lobe agitation blade measuring 3 inches indiameter and mixing was gradually increased until 500 RPM was reachedand a homogeneous mixture resulted. Dibutyltin dilaurate (0.05% by wt.)was then added to the reaction mixture. After approximately 5 minutes ofreaction time and ensuing 10° C. exotherm, a bead of the reactingmixture was applied to one side of each of five aluminum panelsmeasuring 4 in. by 6 in. The beads of solvent-borne polyurethane werethen drawn down each panel into a wet film using a #50 R.D. Specialtiesdrawdown bar to a wet film thickness of 4.5 mils. The panels wereallowed to flash dry in a hood at ambient temperatures for at least onehour, and then heated to 110° C. for 1.5-2 hours to permit completeconversion to polyurethane.

The final dry film thickness was determined using a PosiTector 6000(Defelsko Corporation) dry film thickness gage. Konig hardness wasmeasured using ISO 1522 using a TQC Pendulum Hardness Tester (ModelSPO500). Pencil scratch hardness was measured using ASTM D3363.Flexibility was measured using ASTM D522. Adhesion was measured usingASTM D3359. Stain testing was measured using ASTM D1308. MEK double rubtesting was conducted using ASTM D4752. Table 3 summarizes testing dataon these polyurethane coatings.

Example XXVII Procedure for Preparing Powder Coatings

The following is a procedure for making a powder coating. A 500 mLreactor equipped with an overhead mixer, condenser, heating mantle,thermocouple, and nitrogen inlet is charged with 67.50 g ofpoly(bisphenol A carbonate), 180 g recycled PET pellet, 67.50 gdiethylene glycol, 46.04 g glycerol, and 0.10 g monobutyltin oxidecatalyst and heated with stirring to 200° C. for 8 hours, or until thePET pellets are solubilized. The temperature is then reduced to 100° C.and 142.32 g isophthalic acid is added and the temperature is then setto 175° C. After 1.5 hours the temperature is increased to 185° C.,where it is held for 30 min. The temperature is then increased to 195°C., where it is held for 2 hours. The temperature is further increasedto 205° C. The reaction is continued to run for a total of 25-26 hours,or until the acid value is about 5.5 mg KOH/g. The resultant polyesterpolyol is poured out and allowed to cool, dried and ground a powder.Next 500 g of the ground polyester polyol powder, 300 g titanium dioxidepigment (R-902+ from DuPont), 438 g caprolactam blocked isocyanurate,6.1 g BYK 366P flow agent (an acrylic surface active agent), 3.5 gbenzoin, and 2 g K-Kat 348 bismuth carboxylate catalyst (KingIndustries), are blended in a GlenMills Turbula dyna-MIX blender, andthen extruded through a laboratory scale twin screw extruder with zonetemperatures of 35 and 95° C. The extrudate is cooled, ground, andsieved to provide a fine powder coating having a size of less than 105microns. This powder coating is useful for application to a metalsubstrate using electrostatic or fluidized bed technology.

Example XXVIII Procedure for Making Rigid Polyisocyanurate Foams

The following is a procedure for making a rigid polyisocyanurate foam.The polyester polyol is formulated by weighing the components of thepolyol side of the ingredients (B-side) into a plastic beaker, followedby a 30 second mix using a 4 inch wide Cowles mixing blade. Thecomponents of the B-side include the polyester polyol, water,surfactant, flame retardant, blowing agent and catalysts. The isocyanateside of the ingredients (A-side), includes Papi 27, which is apolymethylene polyphenyl isocyanate that contains MDI (4,4′-methylenediphenyl diisocyante), which is available from the Dow Chemical Co. Anisocyanate/OH equivalent ratio of 2.6/1.0 is used to prepare thepolyisocyanurate foams by weighing the A-side and adding it quickly tothe B-side followed by mixing for 4 seconds at 3000 rpm using a drillpress equipped with a 4 inch Cowles mix blade. The foaming mixture ispoured into a 12″×12″×12″ cardboard box, where the cream, string, riseand tack-free times are recorded. The foam is then tested using standardmethodologies to determine the thermal conductivity, the density and thecompressive strength. The following is a summary of the foamformulation.

Foam Formulation Ingredient Target Weight OH Number Number of Equiv.Polyester Polyol 563.15 282 2.8308 Fyrol PCF¹ 64.00 Dabco K-15² 12.81400 0.0913 Polycat 5³ 1.01 0.0000 Tegostab B8465⁴ 10.10 0.0000 Water2.53 6233  0.2806 n-Pentane 146.41 0.0000 totals 800.00 3.2027 Resin eq.wt. 250 Resin OHV = 224.6 Iso eq. wt. 134 Wt. Ratio (A/B) 1.3948 Partsby Wt. A 58.2 Parts by Wt. B 41.8 NCO/OH index 260.00¹Tris(2-chloroisopropyl)phosphate, ²potassium octoate in diethyleneglycol, ³pentamethyl diethylene triamine, and ⁴silicone surfactant.

Example XXIX Rigid Foam Made from Recycled PolyethyleneTerephthalate(rPET) and Recycled Poly(Bisphenol A Carbonate) r(PBAC)

A rigid foam polyol based on rPET was prepared in a fashion describedabove in Example XXVIII containing 7 wt. % rPBAC. The polyol had ahydroxyl number (OHV) of 266 mg KOH/g, a viscosity of 7408, and an acidvalue of 4.9 mg KOH/g. Using the formulation provided in Example XXVIIIcombined with a 4 second mix using a 3000 rpm drill press equipped witha 4 inch Cowles mix blade, the polyol was converted into apolyisocyanurate foam. A foam cup was used to determine the cup foamdensity. The fine-cell foam had a compressive strength of 36 psi, adensity of 1.99 lb/cu. ft. and a k-factor of 0.172 BTU*in/hr*ft²*° F.(namely British Thermal Units inches per hour square foot degreeFahrenheit).

TABLE 1 Physical Characteristics of the Digestion Product from AromaticPolyacid Sources Acid Source Wt. % Example Polyacid Relative Amounts ofMaterials Used in No. Digestible Aromatic Polyacid Source SourceDigestion Procedure Catalyst 1 PET Pellets 28.74%  1 mole rPET/2.80 molePG/0.46 mole 0.10% Ti(BuO)₄ Dimer Fatty Acid 2 PET Carpet 29.32%  1 molerPET/2.01 mole PG/0.34 mole 0.12% Ti(BuO)₄ Dimer Fatty Acid 3 PTT Carpet30.82%  1 mole rPTT/1.96 mole PG/0.33 mole 0.11% Ti(BuO)₄ Dimer FattyAcid 4 PET Textile (Unbacked) 19.4% 1 mole rPET/1.29 mole PG/0.25 mole0.10% Ti(BuO)₄ Phthalic Anhydride/0.08 mole Soy bean oil 5 PET Textile(Unbacked) - Filtered 19.4% 1 mole rPET/1.29 mole PG/0.25 mole 0.10%Ti(BuO)₄ material of example 4 Phthalic Anhydride/0.08 mole Soy bean oil6 PET Textile (Backed)   15% 1 mole rPET/1.03 mole DEG/0.25 mole 0.10%Ti(BuO)₄ Phthalic Anhydride/0.08 mole Soy bean oil 7 Polyester FiberFill + rPET Pellets 34.91%  1.32 mole rPET/2.8 mole PG/0.46 mole 0.10%Ti(BuO)₄ Dimer Fatty Acid 8 Tritan Copolyester Flakes 20.0% 0.781 moleTritan Copolyester/3.992 0.10% Ti(BuO)₄ mole 1,3-Propanediol/2.502 moleSuccinic Acid 9 PCTA Flake 38.8% 0.85 mole PTCA/0.944 mole NPG/0.7650.15% MTBO mole PG/0.114 mole Glycerol/0.313 mole isopthalic Acid/1.247mole Succinic Acid 10 PCTA Flake 30.0% 0.328 mole PCTA/1.04 moleCHDM/0.181 0.10% Ti(BuO)₄ mole Terephthalic Acid/0.053 mole Dimer FattyAcid Acid Viscosity (cP) at Source 25° C., unless noted Example AcidValue Hydroxyl Value 50% Torque, unless No. (mg KOH/g) (mg KOH/g) ColorSettling Clarity noted 1 0.9 380.0 Amber None Transparent 3097 2 0.8352.0 Dark Amber None Transparent 3000 3 1.0 371.1 Dark Amber NoneSlightly 2307 Transparent 4 1.1 420.7 Dark Purple- Slight, Before Opaque576 Red Filtration 5 1.3 430.0 Dark Purple- None Transparent 588 Red 61.2 338.0 Dark Purple- None Transparent 408 Red 7 0.7 352.0 YellowSlight Opaque 5577 8 0.5 239.0 Grey Filtered Opaque 5800 9 1.2 36.0 GreyFiltered Tranluscent 24,000 (81.57% in n- butyal acetate) 10  0.9 321.7Grey Filtered Opaque Not flowable at 125° C.

TABLE 2 Physical Characteristics of the Digestion Product fromDigestible Polymers Polyol Example Wt. % Digestible No. DigestiblePolymer Polymer Digested Intermediate Catalyst 1 Recycled FlexiblePolyurethane Foam 9.44% 1 mole rPET/3 mole PG/0.5 mole 0.5% Zn(OAc)2present (Carex Health Brands Knee Pillow) Dimer Fatty Acid in digestedintermediate 2 Recycled Polyisocyanurate Insulating 8.68% 1 molerPET/2.8 mole PG/0.46 mole 0.1% Ti(BuO)4 present in Foam Dimer FattyAcid digested intermediate 3 Recycled Flexible Polyurethane Black 9.72%1 mole rPET/2.8 mole PG/0.46 mole 0.1% Ti(BuO)4 present in Foam DimerFatty Acid digested intermediate 4 Recycled Polyisocyanurate Insulating12.62%  Polyol from Example 2 Used to digest Catalyst present from Foamfurther recycled PIR Foam Example 2 5 Recycled Polyisocyanurateinsulating 4.56% 1 mole rPET/2.8 mole PG/0.46 mole 0.1% Ti(BuO)4 presentin foam Dimer Fatty Acid digested intermediate 6 Goose Down Feathers4.37% 1 mole rPET/2.8 mole PG/0.46 mole 0.1% Ti(BuO)4 present in DimerFatty Acid digested intermediate 7 Goose Down Feathers 4.50% 1 molerPET/2.8 mole PG/0.46 mole 0.1% Ti(BuO)4 present in Dimer Fatty Aciddigested intermediate 8 Poly(Bisphenol A Carbonate) 8.80% 1 molerPET/2.8 mole PG/0.46 mole 0.1% Ti(BuO)4 present in Dimer Fatty Aciddigested intermediate 9 Chitin from Shrimp Shells 7.97% 1 mole rPET/2.8mole PG/0.46 mole 0.1% Ti(BuO)4 present in Dimer Fatty Acid digestedintermediate 10 Cellulose 7.93% 1 mole rPET/2.8 mole PG/0.46 mole 0.1%Ti(BuO)4 present in Dimer Fatty Acid digested intermediate 11 Caseinfrom Bovine Milk 7.89% 1 mole rPET/2.8 mole PG/0.46 mole 0.1% Ti(BuO)4present in Dimer Fatty Acid digested intermediate 12 Recycled PolylacticAcid Drinking 9.18% 1 mole rPET/2.8 mole PG/0.46 mole 0.1% Ti(BuO)4present in Cups Dimer Fatty Acid digested intermediate 13 RecycledPolylactic Acid Drinking 25.83%  1 mole rPET/2.8 mole PG/0.46 mole 0.1%Ti(BuO)4 present in Cups Dimer Fatty Acid digested intermediate 14 SoyProtein Acid Hydrolysate 7.70% 1 mole rPET/2.8 mole PG/0.46 mole 0.1%Ti(BuO)4 present in Dimer Fatty Acid digested intermediate 15 Glutenfrom Wheat 8.35% 1 mole rPET/2.8 mole PG/0.46 mole 0.1% Ti(BuO)4 presentin Dimer Fatty Acid digested intermediate 16 Recycled Polyurethane Foam(UFP 10.79%  1 mole rPET/2.8 mole PG/0.46 mole 0.1% Ti(BuO)4 present inTechnologies Polyether Black 30 ppi) Dimer Fatty Acid digestedintermediate 17 Nylon-6 5.39% 1 mole rPET/2.8 mole PG/0.46 mole 0.1%Ti(BuO)4 present in Dimer Fatty Acid digested intermediate 18 RecycledFlexible Polyurethane Foam 9.44% 1 mole rPET/2.8 mole PG/0.46 mole 0.1%Ti(BuO)4 present in (Carex Health Brands Knee Pillow) Dimer FattyAcid/0.002 mole Cardura digested intermediate E10P 19 Chitin from shrimpshells 9.40% Diethylene Glycol None 20 Goose Down Feathers 4.67%Diethylene Glycol None 21 Recycled Flexible Polyurethane Foam 11.58%  1mole rPET/2.8 mole PG/0.46 mole 0.1% Ti(BuO)4 present in (Carex HealthBrands Knee Pillow) Dimer Fatty Acid digested intermediate 22 Goose DownFeathers 8.50% 1 mole rPET/2.8 mole PG 0.1% Ti(BuO)4 23 Goose DownFeathers 5.34% 1 mole rPET/2.8 mole PG/0.46 mole Catalyst present from(Dimer Fatty Acid added after feathers Example 22 digested.) 24 GooseDown Feathers 44.93%  Diethylene Glycol None 25 Goose Down Feathers37.07%  Diethylene Glycol/40 wt. % Ricinoleic None Acid 26 RecycledDuPont Sorona PTT Cloth 9.62% 1 mole rPET/2.8 mole PG/0.46 mole 0.1%Ti(BuO)4 present in (Blue) Dimer Fatty Acid digested intermediate 27Goose Down Feathers 49.55%  Diethylene Glycol None 28 HyPep ® 4601Protein Hydrolysate 10.57%  1 mole rPET/2.8 mole PG/0.46 mole 0.1%Ti(BuO)4 present in from wheat gluten Dimer Fatty Acid digestedintermediate 29 Poly(Bisphenol A Carbonate) 25.10%  1 mole rPET/2.8 molePG/0.46 mole 0.1% Ti(BuO)4 present in Dimer Fatty Acid digestedintermediate 30 Zein from Corn 10.95%  1 mole rPET/2.8 mole PG/0.46 mole0.1% Ti(BuO)4 present in Dimer Fatty Acid digested intermediate 31 SoyProtein Isolate 11.17%  1 mole rPET/2.8 mole PG/0.46 mole 0.1% Ti(BuO)4present in Dimer Fatty Acid digested intermediate 32 Waste ChickenFeathers 5.45% 1 mole rPET/2.8 mole 3-Methyl-1,5- 0.1% Ti(BuO)4Pentanediol/0.3 Dimer Fatty Acid 33 Cellulose 6.83% 3.0 EG/1 rPETflake/1.2 Maleic Acid 0.1% Ti(BuO)4 34 Potato Starch 10.02%  1.0 molerPET flake/3.0 mole PG/0.001 0.1% Ti(BuO)4/0.11% p- mole diethanolamineToluene Sulfonic Acid 35 Chitin from Shrimp Shells 7.44% 1 mole rPETflake/3.0 mole EG/1.2 0.1% Ti(BuO)4 Maleic Acid 36 Cellulose 7.23% 1mole rPET/2.8 mole PG/1.0 mole 0.1% Ti(BuO)4 Succinic Acid 37 Cellulose7.05% 1 mole rPET flake/3 mole PG/1.1 0.1% Ti(BuO)4 Maleic Acid 38Poly(Bisphenol A Carbonate) 12.59%  87.41% Stepanol 2352 (ContainsPhthalic Unknown Anhydride and Diethylene Glycol) 39 Nylon-6,12 9.25% 1mole rPET/2.8 mole PG/0.46 mole 0.1% Ti(BuO)4 present in Dimer FattyAcid digested intermediate 40 Nylon-6,6 Carpet 12.5% 0.68 mole DEG/1.00mole PG/0.49 0.1% Ti(BuO)4 mole Phthalic Anhydride/0.15 mole Soy beanoil 41 Pectin 23.5% 1 mole rPET/2.8 mole PG/0.36 mole 0.1% Ti(BuO)4Dimer Fatty Acid 42 Recycled Poly(Bisphenol A  9.0% 1 mole rPET/1.10mole PG/0.06 mole 0.1% Ti(BuO)4 Carbonate) (Example XVIII) Cargill BiOH5300 (Vegetable Oil based)/ 0.75 mole Succinic Acid 43 RecycledPoly(Bisphenol A 15.0% 85 wt % Stepanpol PN 110 (neopentyl NA Carbonate)(Example XIX) glycol-phthalic anhydride-based polyester polyol) 44Recycled Poly(Bisphenol A  8.0% 1 mole rPET/0.78 mole PG/0.16 mole 0.1%MTBO (Butyltin Carbonate) (Example XX) Trimethylolpropane/0.48 moleSuccinic hydroxide oxide Acid/0.10 mole Dimer Fatty Acid hydrate) 45Recycled Poly(Bisphenol A  9.0% 65 wt % Polyol Example 42/30 wt % 0.1%Ti(BuO)4 present in Carbonate) (Example XXI) Linoleic Acid/5 wt %Glycerol digested intermediate 46 Recycled Poly(Bisphenol A 19.5% 1 molerPET/0.78 mole Neopentyl 0.1% MTBO (Butyltin Carbonate) (Example XXII)Glycol/0.63 mole PG/0.1 mole Glycerol/ hydroxide oxide 0.26 moleIsophthalic Acid/1.03 mole hydrate) Succinic Acid 47 Poly(Bisphenol ACarbonate) 9.37% 0.781 mole Tritan Copolyester/3.992 0.1% Ti(BuO)4present in mole 1,3-Propanediol/2.502 mole digested intermediateSuccinic Acid 48 Poly(Bisphenol A Carbonate) 9.47% 0.85 mole PCTA/0.944mole Neopentyl 0.1% MTBO (Butyltin Glycol/0.765 mole PG/0.114 molehydroxide oxide Glycerol/0.313 mole Isopthalic Acid/ hydrate) 1.247 moleSuccinic Acid 49 Poly(Bisphenol A Carbonate) 9.04% 0.469 mole PCTA/1.04mole CDHM/ 0.1% Ti(BuO)4 present in 0.181 mole Terephthalic Acid/0.053digested intermediate mole Dimer Fatty Acid Viscosity (cP) at Polyol 25°C., unless noted Example Acid Value OHV (mg 50% Torque, unless No. mgKOH/g KOH/g) Color Settling Clarity noted  1 4.0 324.0 Green-amber NoneOpaque 4535  2 1.2 238.3 Brown-amber Slight Semi- 1836 (50° C.)transparent  3 0.4 290.8 Black-amber Slight Opaque 5543  4 0.4 120.4Brown-amber Slight Semi- 22380 (50° C.) transparent  5 0.4 322.7Black-amber None Dark 8769  6 1.1 323.2 Black-red None (filtered) Dark7378  7 1.2 323.6 Black-red None Dark 6586  8 2.5 356.8 Amber NoneTransparent 5745  9 1.4 330.7 Dark brown None Opaque 7483 10 1.3 326.6Brown Yes Opaque 4649 11 3.5 363.3 Dark amber Slight Dark 6546 12 0.5338.8 Amber None Transparent 3954 13 0.4 255.5 Amber None Transparent7013 14 7.7 371.1 Dark red None Dark 6023 15 4.2 360.2 Dark red NoneDark 7956 16 0.6 309.3 Dark red None Transparent 7468 17 1.2 399.3Mustard None Opaque 1023 (100° C.) yellow 18 0.3 363.2 Amber NoneTransparent 2999 19 1.1 957.8 Dark brown Slight Opaque 396.4 20 3.11000.2 Dark red- None Dark 42 (35% torque) brown 21 1.2 321.3 Dark greenNone Opaque 8098 22 2.1 666.2 Dark None Dark 2946 brown/black 23 2.8336.4 Dark None Dark 7113 brown/black 24 25.7 622.1 Dark None Dark 3488brown/black 25 14.0 369.9 Dark None Dark 980.2 brown/black 26 0.7 279.1red-pink None Opaque 14937 27 2.5 472.1 Dark Solidified at Dark —brown/black room temp. 28 6.1 333.6 Dark None Dark 11767 brown/black 293.1 283.6 Amber/Golden None Transparent 12090 30 2.6 345.6 Dark brownNone Dark 10218 31 2.7 306.1 Brown Slight, Thick at Opaque 10964 roomtemp. 32 4.4 469.6 Dark None Dark 1825 brown/amber 33 12.0 347.3 BrownNone, Solidified Opaque 149.7 (125° C.) at room temp. 34 6.4 396.7 Darkbrown None Dark 5632 35 4.2 259.4 Dark brown None, Solidified Opaque3023 (150° C.) at room temp. 36 1.1 340.2 Brown None Opaque 14277 37 1.2289.0 Brown None Opaque 5488 (50° C.) 38 7.4 220.0 Orange NoneTransparent 15207 39 1.4 312.4 Dark yellow None, Solidified Opaque 3453(125° C.) at room temp. 40 2 353.7 Brown None, After Opaque 601filtration 41 1.7 228.3 Brown None, After Transparent 5733 filtration 424.1 134.1 Dark Amber None Transparent 9000 (100° C.) 43 1.9 73.6 WhiteNone Opaque 9410 (100° C.) 44 1.8 93.6 Green None Translucent 31056 (Cutwith Xylene) 45 4.2 91.2 Golden None Transparent 5768 (50° C.) 46 5 75.3Green None Translucent — 47 4.6 202.1 Yellow-gold None Transparent17,496 48 3.7 36.4 Green None Opaque — 49 3.3 255.0 Light Grey NoneOpaque —

TABLE 3 Physical Characteristics of Coatings Made from DigestiblePolymers Konig Pendulum Konig Polyol Coating Hardness, Pendulum Pencil 1hr. Example Thickness, Avg. Hardness, Hardness, Adhesion, Mustard No.Digestible Polymer mil. Oscillations Avg. Sec. Avg. Avg. Resistance 5Recycled Polyisocyanurate 2.27 51 71.6 H 5B 4 Insulating Foam 6 GooseDown Feathers 2.45 42 58.5 H 5B 4 8 Poly(Bisphenol A 2.11 84 118.5 H 5B5 9 Chitin from Shrimp Shells 2.21 45 63.1 H 5B 4 12 Recycled PolylacticAcid 2.08 63 89.0 H 5B 5 Drinking Cups 14 Soy protein acid 2.27 57 79.6H 5B 4 hydrolysate 16 Recycled Polyurethane 2.21 24 33.6 H 5B 4 Foam(UFP Technologies Polyether Black 30 ppi) 17 Nylon 6 2.06 61 85.4 H 5B 421 Recycled Flexible 2.31 57 82.4 H 5B 4 Polyurethane Foam (Carex HealthBrands Knee 29 Poly(Bisphenol A 1.89 109 152.7 H 5B 5 30 Zein from Corn1.63 67 94.6 H 0B 5 32 Waste Chicken Feathers 1.34 84 117.5 H 5B 4 34Potato Starch 1.21 134 188.8 2H 4.5B 5 37 Cellulose 1.54 137 192.9 3H 5B5 38 Poly(Bisphenol A 1.31 9 12.1 H 0B 3 41 Pectin 1.71 74 104.5 3B 5B —42 Recycled Poly(Bisphenol A 0.99 133 186.9 HB 5B — Carbonate) (ExampleXV) 43 Recycled Poly(Bisphenol A 1.04 126 176 HB 5B — Carbonate)(Example XVI) 44 Recycled Poly(Bbisphenol 0.85 115 161.5 B 5B — ACarbonate) (Example XVII) 46 Recycled Poly(Bisphenol A 0.87 159 223 HB5B — Carbonate) (Example XIX) 1 hr. 100 Polyol 1 hr. 1 hr. proof 24 hr.DI MEK ⅛″ Example Sunscreen Windex Vodka Water Double Mandrel No.Resistance Resistance Resistance Resistance Rubs Test  5 5 5 4 5 36 P  64 5 3 4 20 P  8 5 5 5 4 31 P  9 5 4 5 5 35 P 12 5 5 4 4 29 F 14 5 5 3 430 F 16 4 4 3 4 14 P 17 5 5 4 5 68 P 21 5 5 4 5 72 P 29 5 5 4 5 5 F 30 55 4 5 11 P 32 3 5 1 1 6 P 34 5 4 2 5 5 F 37 5 5 5 5 73 F 38 4 5 1 3 9 P41 5 5 5 5 24.5 P 42 5 5 5 5 26 P 43 5 5 5 5 33 F 44 5 5 5 5 25.5 P 46 55 5 5 16 P

INCORPORATION BY REFERENCE

The entire disclosure of each of the patent documents, includingcertificates of correction, patent application documents, scientificarticles, governmental reports, websites, and other references referredto herein is incorporated by reference herein in its entirety for allpurposes. In case of a conflict in terminology, the presentspecification controls.

Equivalents

The invention can be embodied in other specific forms without departingfrom the spirit or essential characteristics thereof. The foregoingembodiments are to be considered in all respects illustrative ratherthan limiting on the invention described herein. In the variousembodiments of the methods and systems of the present invention, wherethe term comprises is used with respect to the recited steps orcomponents, it is also contemplated that the methods and systems consistessentially of, or consist of, the recited steps or components. Further,it should be understood that the order of steps or order for performingcertain actions is immaterial so long as the invention remains operable.Moreover, two or more steps or actions can be conducted simultaneously.

In the specification, the singular forms also include the plural forms,unless the context clearly dictates otherwise. Unless defined otherwise,all technical and scientific terms used herein have the same meaning ascommonly understood by one of ordinary skill in the art to which thisinvention belongs. In the case of conflict, the present specificationwill control.

Furthermore, it should be recognized that in certain instances acomposition can be described as being composed of the components priorto mixing, because upon mixing certain components can further react orbe transformed into additional materials.

All percentages and ratios used herein, unless otherwise indicated, areby weight.

1-20. (canceled)
 21. A polyester polyol comprising recurring unitsgenerated from: (a) an aromatic polyacid source, and (b) a digestiblepolymer containing a functional group selected from an ester, amide,ether, carbonate, urea, carbamate, glycoside, and isocyanurate group, orcombinations thereof.
 22. A polyester polyol according to claim 21,wherein the molar ratio of glycol to aromatic polyacid source is atleast 0.8:1, and the polyol has a hydroxyl number within the range ofabout 10 to about 800 mg KOH/g.
 23. The polyester polyol according toclaim 22 having a viscosity at 125° C. less than about 5000 cP.
 24. Apolyester polyol according to claim 21 further comprising recurringunits of a glycol.
 25. The polyester polyol according to claim 24wherein the glycol is selected from ethylene glycol, propylene glycol,1,3-propanediol, 1,2-butylene glycol, 1,3-butylene glycol,1,4-butanediol, 2-methyl-1,3-propanediol, neopentyl glycol, glycerol,trimethylolpropane, 3-methyl-1,5-pentanediol, 1,4-cyclohexanedimethanol,diethylene glycol, tetraethylene glycol, dipropylene glycol, triethyleneglycol, tripropylene glycol, polyethylene glycol, polypropylene glycol,erythritol, pentaerythritol, sorbitol, and block or random copolymerglycols of ethylene oxide and propylene oxide, or combinations thereof.26. The polyester polyol according to claim 24 wherein the glycolcomprises a recycled glycol.
 27. A polyester polyol according to 21wherein the polyacid source is other than orthophthalic acid or phthalicanhydride.
 28. A polyester polyol according to claim 21 wherein, (a)when the polyacid source is selected from terephthalic acid, isophthalicacid, and orthophthalic acid, or esters or anhydrides thereof, orcombinations of said acids, esters, or anhydrides thereof, (b) thedigestible polymer contains a functional group selected from an ester,amide, ether, carbonate, urea, carbamate, glycoside, and isocyanuarategroup, or combinations thereof.
 29. A polyester polyol according toclaim 21 wherein, (a) when the polyacid source is selected fromterephthalic acid, isophthalic acid, or esters thereof, or combinationsof said acids or esters thereof, (b) the digestible polymer contains afunctional group selected from an ester, amide, ether, carbonate, urea,carbamate, glycoside, and isocyanurate group, or combinations thereof.30. A polyester polyol according to claim 21 further comprising ahydrophobe or nonionic surfactant, or combinations thereof.
 31. Apolyester polyol according to claim 30 wherein the wherein thehydrophobe or nonionic surfactant is selected from ricinoleic acid,castor oil, ethoxylated castor oil, saturated or unsaturated C₉-C₁₈dicarboxylic acids, vegetable oils, fatty acids, fatty acid esters,modified vegetable oils, fatty triglycerides, cardanol-based products,recycled cooking oil, isostearyl alcohol, hydroxy-functional materialsderived from epoxidized, ozonized, or hydroformylated fatty esters,dimer fatty acids, block copolymers of ethylene oxide with propyleneoxide, alkoxylated alkyl phenols, alkoxylated fatty alcohols, orcombinations thereof.
 32. A polyester polyol comprising recurring unitsfrom: (a) an aromatic polyacid source selected from phthalic acid,phthalic anhydride, dimethyl phthalates, dialkyl phthalates,terephthalic acid, dimethyl terephthalates, dialkyl terephthalate,isophthalic acid, dimethyl isophthalates, dialkyl isophthalates,dimethyl terephthalate, dimethyl terephthalate bottoms, trimelliticacid, trimellitic anhydride, trimethyl trimellitate, naphthalenedicarboxylic acid, pyromellitic anhydride, 2,5-furandicarboxylic acid,dialkyl 2,5-furandicarboxylate, pyromellitic acid, dialkyl naphthalenedicarboxylate, and mixtures thereof; (b) a glycol; and (c) a digestiblepolymer containing a functional group selected from an ester, amide,ether, carbonate, urea, carbamate, glycoside, and isocyanurate group, orcombinations thereof; wherein the molar ratio of glycol to aromaticpolyacid source is at least 0.8:1, and the polyol has a hydroxyl numberwithin the range of about 10 to about 800 mg KOH/g.
 33. The polyesterpolyol according to claim 32 wherein the glycol is selected fromethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butylene glycol,1,3-butylene glycol, 1,4-butanediol, 2-methyl-1,3-propanediol, neopentylglycol, glycerol, trimethylolpropane, 3-methyl-1,5-pentanedial,1,4-cyclohexanedimethanol, diethylene glycol, tetraethylene glycol,dipropylene glycol, triethylene glycol, tripropylene glycol,polyethylene glycol, polypropylene glycol, erythritol, pentaerythritol,sorbitol, and block or random copolymer glycols of ethylene oxide andpropylene oxide, or combinations thereof.
 34. The polyester polyolaccording to claim 32 wherein the glycol comprises a recycled glycol.35. The polyester polyol according to claim 32 having a viscosity at125° C. less than about 5000 cP.
 36. A polyester polyol made by aprocess comprising: (a) heating an aromatic polyacid source selectedfrom phthalic acid, phthalic anhydride, dimethyl phthalates, dialkylphthalates, terephthalic acid, dimethyl terephthalates, dialkylterephthalate, isophthalic acid, dimethyl isophthalates, dialkylisophthalates, dimethyl terephthalate, dimethyl terephthalate bottoms,trimellitic acid, trimellitic anhydride, trimethyl trimellitate,naphthalene dicarboxylic acid, pyromellitic anhydride,2,5-furandicarboxylic acid, dialkyl 2,5-furandicarboxylate, pyromelliticacid, dialkyl naphthalene dicarboxylate, and mixtures thereof with aglycol to give a digested intermediate; and (b) reacting the resultingdigested intermediate with a digestible polymer containing a functionalgroup selected from an ester, amide, ether, carbonate, urea, carbamate,glycoside, and isocyanurate, or combinations thereof; wherein the molarratio of glycol to aromatic polyacid source is at least 0.8, and thepolyol has a hydroxyl number within the range of about 10 to about 800mg KOH/g.
 37. The polyester polyol according to claim 36 wherein theglycol is selected from ethylene glycol, propylene glycol,1,3-propanediol, 1,2-butylene glycol, 1,3-butylene glycol,1,4-butanediol, 2-methyl-1,3-propanediol, neopentyl glycol, glycerol,trimethylolpropane, 3-methyl-1,5-pentanedial, 1,4-cyclohexanedimethanol,diethylene glycol, tetraethylene glycol, dipropylene glycol, triethyleneglycol, tripropylene glycol, polyethylene glycol, polypropylene glycol,erythritol, pentaerythritol, sorbitol, and block or random copolymerglycols of ethylene oxide and propylene oxide, or combinations thereof.38. The polyester polyol according to claim 36 wherein the glycolcomprises a recycled glycol.
 39. The polyester polyol according to claim36 having a viscosity at 125° C. less than about 5000 cP.